US20080015319A1 - Explosion taming surfactants for the production of perfluoropolymers - Google Patents
Explosion taming surfactants for the production of perfluoropolymers Download PDFInfo
- Publication number
- US20080015319A1 US20080015319A1 US11/457,236 US45723606A US2008015319A1 US 20080015319 A1 US20080015319 A1 US 20080015319A1 US 45723606 A US45723606 A US 45723606A US 2008015319 A1 US2008015319 A1 US 2008015319A1
- Authority
- US
- United States
- Prior art keywords
- alkyl group
- surfactant
- chf
- carbon atoms
- fluorinated
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000004094 surface-active agent Substances 0.000 title claims abstract description 70
- 238000004880 explosion Methods 0.000 title description 8
- 229920005548 perfluoropolymer Polymers 0.000 title description 5
- 238000004519 manufacturing process Methods 0.000 title description 3
- 239000006185 dispersion Substances 0.000 claims abstract description 44
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 41
- 238000000034 method Methods 0.000 claims abstract description 37
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims abstract description 33
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 32
- 125000004430 oxygen atom Chemical group O* 0.000 claims abstract description 24
- 125000000129 anionic group Chemical group 0.000 claims abstract description 11
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 11
- 239000001257 hydrogen Substances 0.000 claims abstract description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 10
- 239000000839 emulsion Substances 0.000 claims abstract description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 8
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 7
- 239000011737 fluorine Substances 0.000 claims abstract description 7
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims abstract 3
- 229920002313 fluoropolymer Polymers 0.000 claims description 52
- 239000004811 fluoropolymer Substances 0.000 claims description 50
- 150000001875 compounds Chemical class 0.000 claims description 33
- 239000000178 monomer Substances 0.000 claims description 29
- 239000007787 solid Substances 0.000 claims description 22
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 21
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 150000003839 salts Chemical class 0.000 claims description 17
- 239000003995 emulsifying agent Substances 0.000 claims description 16
- 239000002253 acid Substances 0.000 claims description 15
- -1 polytetrafluoroethylene Polymers 0.000 claims description 14
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 claims description 8
- 239000002736 nonionic surfactant Substances 0.000 claims description 8
- BZPCMSSQHRAJCC-UHFFFAOYSA-N 1,2,3,3,4,4,5,5,5-nonafluoro-1-(1,2,3,3,4,4,5,5,5-nonafluoropent-1-enoxy)pent-1-ene Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)=C(F)OC(F)=C(F)C(F)(F)C(F)(F)C(F)(F)F BZPCMSSQHRAJCC-UHFFFAOYSA-N 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 6
- RRZIJNVZMJUGTK-UHFFFAOYSA-N 1,1,2-trifluoro-2-(1,2,2-trifluoroethenoxy)ethene Chemical compound FC(F)=C(F)OC(F)=C(F)F RRZIJNVZMJUGTK-UHFFFAOYSA-N 0.000 claims description 5
- 150000007513 acids Chemical class 0.000 claims description 5
- BLTXWCKMNMYXEA-UHFFFAOYSA-N 1,1,2-trifluoro-2-(trifluoromethoxy)ethene Chemical group FC(F)=C(F)OC(F)(F)F BLTXWCKMNMYXEA-UHFFFAOYSA-N 0.000 claims description 3
- WUMVZXWBOFOYAW-UHFFFAOYSA-N 1,2,3,3,4,4,4-heptafluoro-1-(1,2,3,3,4,4,4-heptafluorobut-1-enoxy)but-1-ene Chemical compound FC(F)(F)C(F)(F)C(F)=C(F)OC(F)=C(F)C(F)(F)C(F)(F)F WUMVZXWBOFOYAW-UHFFFAOYSA-N 0.000 claims description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Chemical group CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 3
- LVGUZGTVOIAKKC-UHFFFAOYSA-N 1,1,1,2-tetrafluoroethane Chemical compound FCC(F)(F)F LVGUZGTVOIAKKC-UHFFFAOYSA-N 0.000 claims description 2
- UJPMYEOUBPIPHQ-UHFFFAOYSA-N 1,1,1-trifluoroethane Chemical compound CC(F)(F)F UJPMYEOUBPIPHQ-UHFFFAOYSA-N 0.000 claims description 2
- WGZYQOSEVSXDNI-UHFFFAOYSA-N 1,1,2-trifluoroethane Chemical compound FCC(F)F WGZYQOSEVSXDNI-UHFFFAOYSA-N 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 239000004215 Carbon black (E152) Substances 0.000 claims 1
- 239000011248 coating agent Substances 0.000 abstract description 6
- 238000000576 coating method Methods 0.000 abstract description 6
- 239000000758 substrate Substances 0.000 abstract description 4
- 238000006116 polymerization reaction Methods 0.000 description 48
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 45
- 238000007720 emulsion polymerization reaction Methods 0.000 description 33
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 32
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 26
- 239000012071 phase Substances 0.000 description 25
- 238000006243 chemical reaction Methods 0.000 description 19
- 238000004821 distillation Methods 0.000 description 19
- 239000002245 particle Substances 0.000 description 17
- 238000002360 preparation method Methods 0.000 description 16
- 239000003999 initiator Substances 0.000 description 13
- 229920000642 polymer Polymers 0.000 description 13
- 238000010992 reflux Methods 0.000 description 13
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- 150000002148 esters Chemical class 0.000 description 11
- 239000010702 perfluoropolyether Substances 0.000 description 11
- 239000011541 reaction mixture Substances 0.000 description 11
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 description 10
- 239000007789 gas Substances 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- 229920001577 copolymer Polymers 0.000 description 8
- 150000003863 ammonium salts Chemical class 0.000 description 7
- 238000009835 boiling Methods 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 150000003254 radicals Chemical class 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 241001465754 Metazoa Species 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000012546 transfer Methods 0.000 description 6
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 5
- 239000003638 chemical reducing agent Substances 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 125000000876 trifluoromethoxy group Chemical group FC(F)(F)O* 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 4
- 241000700159 Rattus Species 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 231100000693 bioaccumulation Toxicity 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 150000002978 peroxides Chemical group 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 238000007127 saponification reaction Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000010557 suspension polymerization reaction Methods 0.000 description 4
- 210000002700 urine Anatomy 0.000 description 4
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 3
- OMNCMLIVRODHHP-UHFFFAOYSA-N 1,2,3,3,4,4,5,5-octafluoro-1-[1,2,3,3,4,4,5,5-octafluoro-5-(trifluoromethoxy)pent-1-enoxy]-5-(trifluoromethoxy)pent-1-ene Chemical compound FC(OC(F)=C(F)C(F)(F)C(F)(F)C(F)(F)OC(F)(F)F)=C(F)C(F)(F)C(F)(F)C(F)(F)OC(F)(F)F OMNCMLIVRODHHP-UHFFFAOYSA-N 0.000 description 3
- OVOAULABUSUXHV-UHFFFAOYSA-N 2,2,3-trifluoro-3-[1,1,2,2,3,3-hexafluoro-3-(trifluoromethoxy)propoxy]propan-1-ol Chemical compound OCC(F)(F)C(F)OC(F)(F)C(F)(F)C(F)(F)OC(F)(F)F OVOAULABUSUXHV-UHFFFAOYSA-N 0.000 description 3
- 229910021630 Antimony pentafluoride Inorganic materials 0.000 description 3
- 206010019842 Hepatomegaly Diseases 0.000 description 3
- 229920001774 Perfluoroether Polymers 0.000 description 3
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 3
- VBVBHWZYQGJZLR-UHFFFAOYSA-I antimony pentafluoride Chemical compound F[Sb](F)(F)(F)F VBVBHWZYQGJZLR-UHFFFAOYSA-I 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229940125782 compound 2 Drugs 0.000 description 3
- 229940126214 compound 3 Drugs 0.000 description 3
- 229940125898 compound 5 Drugs 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000007701 flash-distillation Methods 0.000 description 3
- 238000007667 floating Methods 0.000 description 3
- 238000005194 fractionation Methods 0.000 description 3
- PGFXOWRDDHCDTE-UHFFFAOYSA-N hexafluoropropylene oxide Chemical compound FC(F)(F)C1(F)OC1(F)F PGFXOWRDDHCDTE-UHFFFAOYSA-N 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- XKBGEWXEAPTVCK-UHFFFAOYSA-M methyltrioctylammonium chloride Chemical compound [Cl-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC XKBGEWXEAPTVCK-UHFFFAOYSA-M 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 3
- 150000004965 peroxy acids Chemical class 0.000 description 3
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical class S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- KHXKESCWFMPTFT-UHFFFAOYSA-N 1,1,1,2,2,3,3-heptafluoro-3-(1,2,2-trifluoroethenoxy)propane Chemical compound FC(F)=C(F)OC(F)(F)C(F)(F)C(F)(F)F KHXKESCWFMPTFT-UHFFFAOYSA-N 0.000 description 2
- PXWZCOGAGRNSPS-UHFFFAOYSA-N 2,2,3,3,4,4-hexafluoro-4-(1,2,2,2-tetrafluoroethoxy)butanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)OC(F)C(F)(F)F PXWZCOGAGRNSPS-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 239000000908 ammonium hydroxide Substances 0.000 description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000037396 body weight Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 125000002843 carboxylic acid group Chemical group 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000012986 chain transfer agent Substances 0.000 description 2
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 description 2
- 229940125904 compound 1 Drugs 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- ZQMIGQNCOMNODD-UHFFFAOYSA-N diacetyl peroxide Chemical compound CC(=O)OOC(C)=O ZQMIGQNCOMNODD-UHFFFAOYSA-N 0.000 description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 230000008030 elimination Effects 0.000 description 2
- 238000003379 elimination reaction Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000004816 latex Substances 0.000 description 2
- 229920000126 latex Polymers 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- CVMIVKAWUQZOBP-UHFFFAOYSA-L manganic acid Chemical compound O[Mn](O)(=O)=O CVMIVKAWUQZOBP-UHFFFAOYSA-L 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000002207 metabolite Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000004530 micro-emulsion Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000010943 off-gassing Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- SNGREZUHAYWORS-UHFFFAOYSA-N perfluorooctanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F SNGREZUHAYWORS-UHFFFAOYSA-N 0.000 description 2
- 239000003444 phase transfer catalyst Substances 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000012286 potassium permanganate Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 2
- 235000010262 sodium metabisulphite Nutrition 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 230000002485 urinary effect Effects 0.000 description 2
- 238000010626 work up procedure Methods 0.000 description 2
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 description 1
- AOSFMYBATFLTAQ-UHFFFAOYSA-N 1-amino-3-(benzimidazol-1-yl)propan-2-ol Chemical compound C1=CC=C2N(CC(O)CN)C=NC2=C1 AOSFMYBATFLTAQ-UHFFFAOYSA-N 0.000 description 1
- XUJLWPFSUCHPQL-UHFFFAOYSA-N 11-methyldodecan-1-ol Chemical compound CC(C)CCCCCCCCCCO XUJLWPFSUCHPQL-UHFFFAOYSA-N 0.000 description 1
- YYXWJNBPHDUWJP-UHFFFAOYSA-N 2,2,3,3,4,4,4-heptafluorobutanoyl fluoride Chemical compound FC(=O)C(F)(F)C(F)(F)C(F)(F)F YYXWJNBPHDUWJP-UHFFFAOYSA-N 0.000 description 1
- FDGCJTUAVVJFMB-UHFFFAOYSA-N 2,2,3,3,4,4,5,5-octafluorohexanedioyl difluoride Chemical compound FC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)=O FDGCJTUAVVJFMB-UHFFFAOYSA-N 0.000 description 1
- MNEZTIJYMZUPMM-UHFFFAOYSA-N 2,2,3,3,4,4-hexafluoro-4-(1,1,1,2,3-pentafluoro-3-oxopropan-2-yl)oxybutanoyl fluoride Chemical compound FC(=O)C(F)(F)C(F)(F)C(F)(F)OC(F)(C(F)=O)C(F)(F)F MNEZTIJYMZUPMM-UHFFFAOYSA-N 0.000 description 1
- KNURRSZDMIXZLO-UHFFFAOYSA-N 2,2,3,3-tetrafluorobutanedioyl difluoride Chemical compound FC(=O)C(F)(F)C(F)(F)C(F)=O KNURRSZDMIXZLO-UHFFFAOYSA-N 0.000 description 1
- PHFJMGZBPBUZQS-UHFFFAOYSA-N 2-(1,1,2,2,3,3,3-heptafluoropropoxy)acetic acid Chemical compound OC(=O)COC(F)(F)C(F)(F)C(F)(F)F PHFJMGZBPBUZQS-UHFFFAOYSA-N 0.000 description 1
- ZQCRIOXXOXFNAS-UHFFFAOYSA-N 2-(1,1,2,2,3,3,4,4,4-nonafluorobutoxy)acetic acid Chemical compound OC(=O)COC(F)(F)C(F)(F)C(F)(F)C(F)(F)F ZQCRIOXXOXFNAS-UHFFFAOYSA-N 0.000 description 1
- WHGFMLVGYMAHGO-UHFFFAOYSA-N 2-(1,1,2,3,3,3-hexafluoropropoxy)acetic acid Chemical compound OC(=O)COC(F)(F)C(F)C(F)(F)F WHGFMLVGYMAHGO-UHFFFAOYSA-N 0.000 description 1
- UAYQEKBPFNNGSX-UHFFFAOYSA-N 2-[1,1,2,2-tetrafluoro-2-(trifluoromethoxy)ethoxy]acetic acid Chemical compound OC(=O)COC(F)(F)C(F)(F)OC(F)(F)F UAYQEKBPFNNGSX-UHFFFAOYSA-N 0.000 description 1
- FLTHVWFEQOTAII-UHFFFAOYSA-N 2-[1,1,2-trifluoro-2-(trifluoromethoxy)ethoxy]acetic acid Chemical compound OC(=O)COC(F)(F)C(F)OC(F)(F)F FLTHVWFEQOTAII-UHFFFAOYSA-N 0.000 description 1
- GHVHGLNEHMMXAV-UHFFFAOYSA-N 2-fluoro-2-[1,1,2,2-tetrafluoro-2-(trifluoromethoxy)ethoxy]acetic acid Chemical compound OC(=O)C(F)OC(F)(F)C(F)(F)OC(F)(F)F GHVHGLNEHMMXAV-UHFFFAOYSA-N 0.000 description 1
- MKTOIPPVFPJEQO-UHFFFAOYSA-N 4-(3-carboxypropanoylperoxy)-4-oxobutanoic acid Chemical compound OC(=O)CCC(=O)OOC(=O)CCC(O)=O MKTOIPPVFPJEQO-UHFFFAOYSA-N 0.000 description 1
- HVXRCAWUNAOCTA-UHFFFAOYSA-N 4-(6-methylheptyl)phenol Chemical class CC(C)CCCCCC1=CC=C(O)C=C1 HVXRCAWUNAOCTA-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- SXWUSKUNDTYYNV-UHFFFAOYSA-N FC(=C(C(C(C(F)(F)F)(OC(C(C(F)(F)F)(F)F)(F)F)F)(F)F)F)OC(=C(F)C(C(C(F)(F)F)(F)OC(C(C(F)(F)F)(F)F)(F)F)(F)F)F Chemical compound FC(=C(C(C(C(F)(F)F)(OC(C(C(F)(F)F)(F)F)(F)F)F)(F)F)F)OC(=C(F)C(C(C(F)(F)F)(F)OC(C(C(F)(F)F)(F)F)(F)F)(F)F)F SXWUSKUNDTYYNV-UHFFFAOYSA-N 0.000 description 1
- GHSBRBCKXUSPAS-UHFFFAOYSA-N FC(=C(C(C(OC(F)(F)F)(F)F)(F)F)F)OC(=C(F)C(C(F)(F)OC(F)(F)F)(F)F)F Chemical compound FC(=C(C(C(OC(F)(F)F)(F)F)(F)F)F)OC(=C(F)C(C(F)(F)OC(F)(F)F)(F)F)F GHSBRBCKXUSPAS-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 238000011887 Necropsy Methods 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical class OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- YKKPYMXANSSQCA-UHFFFAOYSA-N [3-[4-(aminomethyl)-6-(trifluoromethyl)pyridin-2-yl]oxyphenyl]-(3-pyrazol-1-ylazetidin-1-yl)methanone Chemical compound N1(N=CC=C1)C1CN(C1)C(=O)C1=CC(=CC=C1)OC1=NC(=CC(=C1)CN)C(F)(F)F YKKPYMXANSSQCA-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 229940044197 ammonium sulfate Drugs 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 239000012935 ammoniumperoxodisulfate Substances 0.000 description 1
- 239000012491 analyte Substances 0.000 description 1
- 238000010171 animal model Methods 0.000 description 1
- 239000003957 anion exchange resin Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000005604 azodicarboxylate group Chemical group 0.000 description 1
- ZJRXSAYFZMGQFP-UHFFFAOYSA-N barium peroxide Chemical compound [Ba+2].[O-][O-] ZJRXSAYFZMGQFP-UHFFFAOYSA-N 0.000 description 1
- 150000008107 benzenesulfonic acids Chemical class 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 230000002902 bimodal effect Effects 0.000 description 1
- 230000031018 biological processes and functions Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- IWTBWSGPDGPTIB-UHFFFAOYSA-N butanoyl butaneperoxoate Chemical compound CCCC(=O)OOC(=O)CCC IWTBWSGPDGPTIB-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000012933 diacyl peroxide Substances 0.000 description 1
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- 229920001198 elastomeric copolymer Polymers 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
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- 125000001033 ether group Chemical group 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 238000000806 fluorine-19 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 125000003709 fluoroalkyl group Chemical group 0.000 description 1
- 229920001973 fluoroelastomer Polymers 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 239000013529 heat transfer fluid Substances 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 150000002429 hydrazines Chemical class 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 210000004185 liver Anatomy 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- VOKIUIIBMBYXNU-UHFFFAOYSA-N methyl 2,2,3-trifluoro-3-[1,1,2,2,3,3-hexafluoro-3-(trifluoromethoxy)propoxy]propanoate Chemical compound FC(C(=O)OC)(C(OC(C(C(OC(F)(F)F)(F)F)(F)F)(F)F)F)F VOKIUIIBMBYXNU-UHFFFAOYSA-N 0.000 description 1
- GSJFXBNYJCXDGI-UHFFFAOYSA-N methyl 2-hydroxyacetate Chemical compound COC(=O)CO GSJFXBNYJCXDGI-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 238000003305 oral gavage Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 125000006551 perfluoro alkylene group Chemical group 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 229940093914 potassium sulfate Drugs 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- KOPQZJAYZFAPBC-UHFFFAOYSA-N propanoyl propaneperoxoate Chemical compound CCC(=O)OOC(=O)CC KOPQZJAYZFAPBC-UHFFFAOYSA-N 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 231100000161 signs of toxicity Toxicity 0.000 description 1
- 150000003378 silver Chemical class 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 229940001584 sodium metabisulfite Drugs 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 229940001474 sodium thiosulfate Drugs 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 238000013222 sprague-dawley male rat Methods 0.000 description 1
- 239000012258 stirred mixture Substances 0.000 description 1
- 230000000153 supplemental effect Effects 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 150000004764 thiosulfuric acid derivatives Chemical class 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F14/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F14/18—Monomers containing fluorine
- C08F14/26—Tetrafluoroethene
Definitions
- Fluoropolymers i.e. polymers having a fluorinated backbone
- Fluoropolymers have been long known and have been used in a variety of applications because of several desirable properties such as heat resistance, chemical resistance, weatherability, UV-stability etc.
- the various fluoropolymers are for example described in “Modern Fluoropolymers”, edited by John Scheirs, Wiley Science 1997.
- fluoropolymers include polytetrafluoroethylene (PTFE), copolymers of tetrafluoroethylene (TFE) and hexafluoropropylene (HFP) (FEP polymers), perfluoroalkoxy copolymers (PFA), ethylene-tetrafluoroethylene (ETFE) copolymers, terpolymers of tetrafluoroethylene, hexafluoropropylene and vinylidene fluoride (THV) and polyvinylidene fluoride polymers (PVDF) and others.
- PTFE polytetrafluoroethylene
- TFE tetrafluoroethylene
- HFP hexafluoropropylene
- FEP polymers perfluoroalkoxy copolymers
- ETFE ethylene-tetrafluoroethylene copolymers
- Aqueous emulsion polymerization normally involves polymerization in the presence of a fluorinated surfactant.
- the suspension polymerization generally does not involve the use of surfactant but results in substantially larger polymer particles than in case of the aqueous emulsion polymerization.
- the polymer particles formed during suspension polymerization settle out of the reaction mixture whereas the dispersions obtained in emulsion polymerization generally exhibit good stability over a long period of time.
- WO 97/17381 discloses an aqueous emulsion polymerization in the absence of a surfactant wherein a radical initiator system of a reducing agent and oxidizing agent is used to initiate the polymerization and whereby the initiator system is added in one or more further charges during the polymerization. So-called emulsifier free polymerization has further been disclosed in WO 02/88206 and WO 02/88203.
- WO 02/88207 teaches an emulsifier free polymerization using certain chain transfer agents to minimize formation of water-soluble fluorinated compounds.
- An emulsifier free polymerization is further disclosed in RU 2158274 for making an elastomeric copolymer of hexafluoropropylene and vinylidene fluoride.
- the aqueous emulsion polymerization process in the presence of fluorinated surfactants is still a desirable process to produce fluoropolymers because it can yield stable fluoropolymer particle dispersions in high yield and in a more environmental friendly way than for example polymerizations conducted in an organic solvent.
- the emulsion polymerization process is carried out using a perfluoroalkanoic acid or salt thereof as a surfactant.
- surfactants are typically used because they provide a wide variety of desirable properties such as high speed of polymerization, good copolymerization properties of fluorinated olefins with comonomers, small particle sizes of the resulting dispersion, desirable stability, and good polymerization yields, i.e. a high amount of solids can be produced.
- environmental concerns have been raised against these surfactants and moreover these surfactants are generally expensive.
- perfluorinated alkanoic acids having 8 or more carbon atoms are known to be bio-accumulating.
- surfactants of the general formula R f —C 2 H 4 —SO 3 M, wherein R f represents a perfluorinated aliphatic group and wherein M represents a cation have been disclosed in U.S. Pat. No. 5,789,508, U.S. Pat. No. 4,025,709, U.S. Pat. No. 5,688,884 and U.S. Pat. No. 4,380,618.
- U.S. Pat. No. 5,763,552 discloses partially fluorinated surfactants of the general formula R f —(CH 2 ) m —R′ f —COOM wherein R f represents a perfluoroalkyl group or a perfluoroalkoxy group of 3 to 8 carbon atoms, R′ f represents a perfluoroalkylene of 1 to 4 carbon atoms and m is 1-3.
- U.S. Pat. No. 4,621,116 discloses perfluoroalkoxy benzene sulfonic acids and salts thereof in the aqueous emulsion polymerization of fluorinated monomers.
- n 0 to 10.
- the perfluoropolyethers are taught as emulsifiers in the emulsion polymerization of ethylenically unsaturated monomers.
- m 3 to 10
- X is F or a perfluoroalkyl group
- n 0, 1 or 2
- A is the counter ion of the carboxylic anion.
- perfluoropolyethers having neutral end groups in an aqueous emulsion polymerization is disclosed in U.S. Pat. No. 4,864,006, U.S. Pat. No. 4,789,717 and EP 625526.
- U.S. Pat. No. 4,864,006 and EP 625526 disclose the use of microemulsion prepared from perfluoropolyethers having neutral end groups in an aqueous emulsion polymerization of fluorinated monomers.
- a certain perfluoropolyether having carboxylic end groups is taught to emulsify the neutral perfluoropolyether.
- EP 1,334,996 discloses certain perfluoropolyethers having carboxylic acid groups or salts thereof at both end groups, i.e. the perfluoropolyethers are bifunctional.
- the perfluoropolyethers are taught for use in aqueous dispersions of fluoropolymers and in the preparation of such dispersion by aqueous emulsion polymerization.
- WO 00/71590 teaches the use of a combination of perfluoropolyether surfactants having a carboxylic acid group or salt thereof with a fluoroalkyl carboxylic acid or sulfonic acid or salt thereof. It is taught that the perfluoropolyether surfactants on their own are not very powerful surfactants.
- the present invention relates to a process comprising polymerizing tetrafluoroethylene in an aqueous emulsion in the presence of a non-telogenic surfactant having an anionic portion with the general formula (I):
- R f is selected from a partially fluorinated alkyl group, a perfluorinated alkyl group, a partially fluorinated alkyl group interrupted by one or more oxygen atoms, and a perfluorinated alkyl group interrupted by one or more oxygen atoms, wherein R f has from 1 to 10 carbon atoms; and L is an alkylene group having the general formula (CX 2 ) n wherein each X is independently selected from R f , fluorine, and hydrogen and n is selected from1 to 5, with the proviso that the surfactant contains at least one unit selected from a —CH 2 — unit and a —CHF—— unit.
- the present invention relates to an aqueous dispersion of a tetrafluoroethylene-containing perfluoropolymer comprising a non-telogenic surfactant having an anionic portion with the general formula:
- R f is selected from a partially fluorinated alkyl group, a perfluorinated alkyl group, a partially fluorinated alkyl group interrupted by one or more oxygen atoms, and a perfluorinated alkyl group interrupted by one or more oxygen atoms, wherein R f has from 1 to 10 carbon atoms; and L is an alkylene group having the general formula (CX 2 ) n wherein each X is independently selected from R f , fluorine, and hydrogen and n is selected from 1 to 5, with the proviso that the surfactant contains at least one unit selected from a —CH 2 — unit and a —CHF— unit.
- the invention relates to processes to prevent or at least reduce explosions in the production of polytetrafluoroethylene and other perfluoropolymers.
- ether groups may be present in the aliphatic group. That is, for instance, where two oxygen atoms are present, they are separated by at least one carbon atom, so as to form a di-ether. Peroxide structures are not contemplated by the term “interrupted by one or more oxygen atoms”.
- the present inventors recognize the desirability of finding an alternative emulsion polymerization process in which the use of perfluoroalkanoic acids and salts thereof as a fluorinated surfactant can be avoided or at least greatly reduced.
- an alternative surfactant or dispersant in particular one that for example has a low toxicity and/or shows no or only little bioaccumulation.
- the alternative surfactant has good chemical and thermal stability enabling polymerization over a wide range of conditions of for example temperature and/or pressure.
- the alternative surfactant or dispersant allows for a high polymerization rate, good dispersion stability, good yields, good copolymerization properties and/or the possibility of obtaining a wide variety of particle sizes including small particle sizes.
- the properties of the resulting fluoropolymer should generally not be negatively influenced and preferably would be improved.
- the resulting dispersions, concentrated dispersions, and fluoropolymers obtainable from dispersions as described herein have good or excellent properties in coating applications and/or impregnation of substrates, including for example good film forming properties.
- the polymerization can be carried out in a convenient and cost effective way, preferably using equipment commonly used in the aqueous emulsion polymerization of fluorinated monomers. Additionally, it may be desirable to recover the alternative surfactant or dispersant from wastewater streams and/or to remove or recover the surfactant from the dispersion subsequent to the polymerization. Desirably, such recovery can proceed in an easy, convenient and cost effective way. Recovery processes have been reviewed in EP 1514848 and a particular method involves treating the aqueous liquid with adsorbent particles including for example an anion exchange resin as disclosed in EP 1083441, EP 1084097 or other adsorbent particles such as activated carbon particles as disclosed in WO 2005/082785.
- adsorbent particles including for example an anion exchange resin as disclosed in EP 1083441, EP 1084097 or other adsorbent particles such as activated carbon particles as disclosed in WO 2005/082785.
- the processes are typically practiced for recovering perfluorooctanoic acid or salts thereof, which is the most widely used surfactant in making fluoropolymers through aqueous emulsion polymerization. These processes can be adapted to recover the surfactants described herein, having an anionic portion with general formula (I).
- the present invention provides a process comprising polymerizing tetrafluoroethylene in an aqueous emulsion in the presence of a non-telogenic surfactant having an anionic portion with the general formula (I):
- R f is selected from a partially fluorinated alkyl group, a perfluorinated alkyl group, a partially fluorinated alkyl group interrupted by one or more oxygen atoms, and a perfluorinated alkyl group interrupted by one or more oxygen atoms, wherein R f has from 1 to 10 carbon atoms; and L is an alkylene group having the general formula (CX 2 ) n wherein each X is independently selected from R f , fluorine, and hydrogen and n is selected from 1 to 5, with the proviso that the surfactant contains at least one unit selected from a —CH 2 — unit and a —CHF— unit.
- the invention pertains to a safe technology for the production of perfluoropolymers (e.g. PTFE) through aqueous emulsion polymerization of TFE, whereby a significant cause of explosion is avoided.
- TFE is thermodynamically unstable, and decomposes with great reaction enthalpy into carbon and tetrafluoromethane. Under adiabatic and isochoric conditions, the initial pressure increases by 8- to 10-fold during the decomposition.
- the decomposition requires an ignition temperature of about 300° C.
- the invention is based on the knowledge that the explosions start from so-called “hot spots”.
- the “hot spots” form from small amounts of floating fluoropolymer dispersion coagulate.
- the tetrafluoroethylene polymer coagulate floats on the aqueous surface of the polymerization media, despite having a density of more than 2 g/cm 3 . Under these conditions, the coagulate is exposed to an elevated TFE concentration in the gas phase, which causes the polymerization speed to accelerate at the polymer-monomer interface. Concurrently, the cooling at the surface is decreased due to the lack of heat transfer fluid (water).
- TFE polymerization One attribute of TFE polymerization is that the polymer chain radicals cannot terminate themselves because there is no chain transfer of the polymer in which a fluorine atom separates in order to form a terminal double bond. Consequently, the heat-generating radicals are fixed in place within the coagulate surfaces.
- non-telogenic surfactants having the anionic portion with general formula (I), described above do not show significant telogenic activities under standard polymerization conditions for making PTFE.
- standard polymerization conditions is meant at a temperature range of from 0 to 150, for instance from about 10 to 100° C., and at a partial pressure of tetrafluoroethylene of from 2 to 40 bar, for instance, from 5 to 30 bar. Only at very high temperatures, for instance, beyond 300° C., does the non-telogenic surfactant act as chain transfer agent.
- the concentration for the surfactants is typically from 0.005 to 1% by weight based on the amount of fluoropolymer solids in the aqueous dispersion.
- the present invention provides aqueous dispersions of a fluoropolymer comprising a surfactant of formula (I) as the only emulsifier in the composition.
- the resulting dispersions can be used in a variety of applications including coating and impregnation of substrates.
- a non-ionic surfactant should be added to the dispersion for such applications.
- the invention in a further aspect relates to aqueous dispersions of a fluoropolymer comprising a surfactant of formula (I) as an emulsifier and additionally comprising a non-ionic surfactant.
- the non-ionic surfactant is typically present in an amount of from 1 to 12% by weight based on the weight of fluoropolymer solids.
- the aqueous emulsion polymerization of fluorinated monomers can be conducted using one or more surfactants according to formula (I) as an emulsifier.
- the polymerization may be carried out using a mixture of surfactants of formula (I).
- linking groups L may be selected from the following:
- surfactants according to formula (I) are those having anionic portions of the following formulae:
- R f ′ O—CHF—CO 2 —, wherein R f ′ is selected from a perfluorinated alkyl group having from 1 to 10 carbon atoms and a perfluorinated alkyl group interrupted by one or more oxygen atoms and having from 1 to 10 carbon atoms;
- R f ′ O—CHF—CF 2 —CO 2 —, wherein R f ′ is selected from a perfluorinated alkyl group having from 1 to 10 carbon atoms and a perfluorinated alkyl group interrupted by one or more oxygen atoms and having from 1 to 10 carbon atoms;
- R f ′ O—CF 2 —CHF—CO 2 —, wherein R f ′ is selected from a perfluorinated alkyl group having from 1 to 10 carbon atoms and a perfluorinated alkyl group interrupted by one or more oxygen atoms and having from 1 to 10 carbon atoms;
- R f ′ O—CF 2 CHFCF 2 CO 2 — wherein R f ′ is selected from a perfluorinated alkyl group having from 1 to 10 carbon atoms and a perfluorinated alkyl group interrupted by one or more oxygen atoms and having from 1 to 10 carbon atoms;
- surfactants described herein include:
- the surfactant is used in the aqueous emulsion polymerization of tetrafluoroethylene, either as a homopolymer to give polytetrafluoroethylene, as a copolymer with perfluorovinyl ethers (PFA, MFA), or as a copolymer with hexafluoropropylene (FEP).
- PFA perfluorovinyl ethers
- FEP hexafluoropropylene
- Polymerizing tetrafluoroethylene yields a polytetrafluoroethylene (PTFE) that is high in molecular weight and correspondingly has an SSG density (ASTM D 4895-04) of less than 2.25 g/cm 3 (inclusive) and is non melt-processable.
- non-telogenic surfactant refers to a surfactant in the presence of which it is possible to obtain a non-melt processable PTFE having an SSG density (ASTM D 4895-04) of less than 2.25 g/cm 3 (inclusive).
- a PTFE can be prepared with an SSG density of less than 2.20, even less than 2.19, 2.17, or even lower.
- the surfactants described herein allow for the preparation of PTFE having an SSG density comparable to those PTFE's prepared in the presence of perfluorooctanoic acid.
- copolymers of tetrafluoroethylene are also contemplated by the present invention. These copolymers may include, in addition to tetrafluoroethylene, one or more fluorinated monomers, in particular gaseous fluorinated monomers.
- fluorinated monomers in particular gaseous fluorinated monomers.
- gaseous fluorinated monomers monomers that are present as a gas under the polymerization conditions.
- the polymerization of the tetrafluoroethylene, optionally in the presence of one or more additional fluorinated monomers is initiated in the presence of the surfactant of formula (I), for instance, in an aqueous emulsion polymerization.
- the amount of surfactant of formula (I) may vary depending on the desired properties of the resulting aqueous dispersion, such as the amount of solids, the fluoropolymer particle size, and the like. Generally, the amount of surfactant of formula (I) will be from 0.005% by weight based on the weight of fluoropolymer solids in the aqueous emulsion to 1% by weight; for example, from 0.01% by weight and 0.75% by weight. Some embodiments have a range of from 0.1% by weight to 0.5% by weight.
- the anionic portion of the partially fluorintated carboxylic acid used in the process of the invention corresponds to formula (I).
- the fluorinated carboxylic acid anion will be a low molecular weight compound, for example a compound having a molecular weight of not more than 1000 g/mol, typically not more than 600 g/mol and in particular embodiments, the fluorinated carboxylic acid anion may have a molecular weight of not more than 500 g/mol.
- the polymerization may be initiated in the presence of the surfactant of formula (I), it is also contemplated that the surfactant of formula (I) is added during the polymerization.
- aqueous emulsion it may, for instance, be desirable to add certain monomers to the polymerization in the form of an aqueous emulsion.
- fluorinated monomers and in particular perfluorinated co-monomers that are liquid under the polymerization conditions may be added to the polymerization in the form of an aqueous emulsion of the monomer.
- emulsions may be prepared using the surfactant of formula (I) or by using a different surfactant.
- the emulsions of monomer prepared and added to the polymerization may be in the form of a micro-emulsion.
- the aqueous emulsion polymerization may be carried out at a temperature of from 0 to 150° C.
- the temperature may be from 10° C. and higher, from 20° C. and higher, even from 30° C. and higher.
- the temperature may be up to 100° C., up to 90° C., even up to 80° C.
- the partial pressure of tetrafluoroethylene in the headspace of the reactor is typically from 5 to 30 bar, in particular, from 5 to 20 bar.
- the reaction temperature may be varied during the polymerization to influence the molecular weight distribution, e.g., to obtain a narrow or broad molecular weight distribution or to obtain a bimodal or multimodal molecular weight distribution.
- the aqueous emulsion polymerization is typically initiated by an initiator including any of the initiators known for initiating a free radical polymerization of fluorinated monomers.
- Suitable initiators include peroxides and azo compounds and redox based initiators.
- Specific examples of peroxide initiators include, hydrogen peroxide, sodium or barium peroxide, diacylperoxides such as diacetylperoxide, disuccinoyl peroxide, dipropionylperoxide, dibutyrylperoxide, diglutaric acid peroxide, and further per-acids and salts thereof such as e.g. ammonium, sodium or potassium salts.
- per-acids include peracetic acid. Esters of the peracid can be used as well.
- examples of inorganic initiators include for example ammonium- alkali- or earth alkali salts of persulfates, permanganic or manganic acid or manganic acids.
- a persulfate initiator e.g. ammonium persulfate (APS) may be used alone or may be used in combination with a reducing agent.
- Suitable reducing agents include bisulfites such as for example ammonium bisulfite or sodium metabisulfite, thiosulfates such as for example ammonium, potassium or sodium thiosulfate, hydrazines, azodicarboxylates and azodicarboxyldiamide (ADA).
- Further reducing agents that may be used include sodium formaldehyde sulfoxylate (Rongalit®, available from BASF, Germany) or fluoroalkyl sulfinates. The reducing agent typically reduces the half-life time of the persulfate initiator.
- a metal salt catalyst such as for example copper, iron or silver salts may be added.
- the amount of initiator may be from 0.0001% by weight (based on the fluoropolymer solids to be produced) to 1% by weight. In one embodiment, the amount of initiator is from 0.0005 to 0.5% by weight. In another embodiment, the amount may be from 0.005 to 0.3% by weight.
- the aqueous emulsion polymerization system may further comprise other materials, such as buffers and, if desired, complex-formers or chain-transfer agents.
- chain transfer agents are typically present in small amounts so as to not interfere with the preparation of high molecular weight polymers.
- chain transfer agents that can be used include ethers, such as dimethyl ether, and methyl t-butyl ether; alkanes having 1 to 5 carbon atoms such as ethane, propane and n-pentane; halogenated hydrocarbons such as CCl 4 , CHCl 3 and CH 2 Cl 2 and hydrofluorocarbon compounds; and alcohols.
- fluorinated compounds that may be present during the polymerization, which may or may not act as a chain transfer agent, include organic, saturated, hydrogen—containing fluorinated compounds that have a water solubility at 25° C. of from 1 ⁇ 10 ⁇ 3 (mol/l*bar) to 4 ⁇ 10 ⁇ 3 (mol/l*bar). Such compounds may be useful in suppressing explosions by providing supplemental quenching of “hot spots”. Such fluorinated compounds are typically present at a partial pressure of from 2.5 mbar to 0.5 bar. These compounds may, in some embodiments, be partially fluorinated hydrocarbons that contain chlorine or ether bridges. In other embodiments, the fluorinated compounds contain at least one —CH 2 — group or at least one —CH 3 group. In yet further embodiments, the fluorinated compounds are selected from 1,1,1-trifluoroethane, 1,1,2-trifluoroethane, 1,1,1,2-tetrafluoroethane, and combinations thereof.
- the present invention is best suited for the TFE—homopolymerization, and in particular for making high molecular weight PTFE as well as modified PTFE, it is also applicable to other perfluorinated copolymers as described herein.
- fluorinated gaseous monomers including fluorinated olefins such as tetrafluoroethylene, chlorotrifluoroethylene, hexafluoropropylene, fully fluorinated allyl ethers and fully fluorinated vinyl ethers.
- fluorinated monomers that may be used in the aqueous emulsion polymerization according to the invention include those corresponding to the formula:
- R f in formula (II) represents a perfluorinated aliphatic group that may contain one or more oxygen atoms.
- the perfluorovinyl ethers of formula (II) correspond to the general formula:
- R f and R′ f in formula (III) are different linear or branched perfluoroalkylene groups of from 2 to 6 carbon atoms, m and n are each independently from 0 to 10, and R′′ f is a perfluoroalkyl group of from 1 to 6 carbon atoms.
- perfluorovinyl ethers examples include perfluoro-2-propoxypropylvinyl ether (PPVE-2), perfluoro-3-methoxy-n-propylvinyl ether, perfluoro-2-methoxy-ethylvinyl ether, perfluoromethylvinyl ether (PMVE), perfluoroethylvinyl ether (PEVE), perfluoropropylvinyl ether (PPVE), perfluoro-n-propylvinyl ether (PPVE-1) and CF 3 —(CF 2 ) 2 —O—CF(CF 3 )—CF 2 —O—CF(CF 3 )—CF 2 —O—CF ⁇ CF 2 .
- the aqueous emulsion polymerization may be used to produce a variety of fluoropolymers including perfluoropolymers. Also the aqueous emulsion polymerization may result in melt—processable fluoropolymers as well as those that are not melt-processable. Obtainable polymers include, for example, polytetrafluoroethylene and so-called modified polytetrafluoroethylene.
- the aqueous emulsion polymerization results in a dispersion of the fluoropolymer in water.
- the amount of solids of the fluoropolymer in the dispersion directly resulting from the polymerization will vary from 3% by weight to 40% by weight, depending on the polymerization conditions.
- a typical range is from 5 to 35%, for instance, from 10 to 30% by weight.
- the particle size (volume average particle size) of the fluoropolymer may be from 50 nm to 350 nm, with a typical particle size being from 100 nm to 300 nm.
- the amount of surfactant having an anionic portion with the general formula (I) in the resulting dispersion is typically from 0.005 to 1% by weight based on the weight of fluoropolymer solids in the aqueous dispersion.
- a typical amount may be from 0.01 to 0.75% by weight or from 0.1 to 0.5% by weight, based on the weight of the fluoropolymer solids.
- the fluoropolymer may be isolated from the dispersion by coagulation if a polymer in solid form is desired. Also, depending on the requirements of the application in which the fluoropolymer is to be used, the fluoropolymer may be post-fluorinated so as to convert any thermally unstable end groups into stable CF 3 end groups. Generally, when the fluoropolymer is post fluorinated, it is post fluorinated such that the amount of end groups in the fluoropolymer other than CF 3 is less than 80 per million carbon atoms.
- an aqueous dispersion of the fluoropolymer may be desired and hence the fluoropolymer may not need to be separated or coagulated from the dispersion.
- further stabilizing surfactants may be added and/or the level of fluoropolymer solids may be increased.
- non—ionic stabilizing surfactants may be added to the fluoropolymer dispersion. Typically these will be added to an aqueous fluoropolymer dispersion in an amount of 1 to 12% by weight based on fluoropolymer solids. Examples of non-ionic surfactants that may be added include
- R 1 represents an aromatic or aliphatic hydrocarbon group (linear or branched) having at least 8 carbon atoms
- R 2 represents an alkylene having 3 carbon atoms
- R 3 represents hydrogen or a C 1 -C 3 alkyl group
- n has a value of 0 to 40
- m has a value of 0 to 40 and the sum of n+m being at least 2.
- non—ionic surfactants according to formula (V) above include alkylphenol ethoxylates such as ethoxylated p-isooctylphenol commercially available under the brand name TRITONTM such as for example TRITONTM X100 wherein the number of ethoxy units is about 10 or TRITONTM X114 (available from Dow Chemical, Midland, Mich.) wherein the number of ethoxy units is about 7 to 8.
- R 1 in the above formula (V) represents an alkyl group of 4 to 20 carbon atoms, m is 0 and R 3 is hydrogen.
- Non-ionic surfactants according to formula (V) in which the hydrophilic part comprises a block-copolymer of ethoxy groups and propoxy groups may be used as well.
- Such non-ionic surfactants are commercially available from Clariant GmbH under the trade designation GENAPOL®PF 40 and GENAPOL®PF 80.
- the amount of fluoropolymer solids in the dispersion may be up-concentrated as needed or desired to an amount between 30 and 70% by weight. Any of the known up-concentration techniques may be used including ultra-filtration and thermal up-concentration.
- the surfactant may be removed or reduced from fluoropolymer dispersions described herein.
- the methods for removal include those generally known in the art including those described in U.S. Pat. No. 6,833,403, Blädel, et al.
- fluoropolymers and fluoropolymer dispersions made from the processes described herein include those commonly known for fluoropolymers. These applications include, for instance, those described in “Fluoroplastics: Vol. 1, Non-Melt Processible Fluoroplastics”, Ebnesajjad, Chapter 17 (2000).
- the inventors have also found that the reduced risk of explosion associated with polymerization processes carried out as described herein allows for polymerization on a commercial scale to be carried out in larger reactors and at higher solids content than is safely achieved under previously employed polymerization processes.
- the latex particle size determination was conducted by means of dynamic light scattering with a Malvern Zetasizer 1000 HAS in accordance to ISO/DIS 13321. Prior to the measurements, the polymer latexes as yielded from the polymerizations were diluted with 0.001 mol/L KCl-solution, the measurement temperature was 25° C. in all cases. The reported average is the Z-average particle diameter.
- the polymerization experiments were performed in a 40 l kettle equipped with an impeller agitator and a baffle.
- the kettle was charged with 30 l of deionized water and set to 35° C.; the kettle was evacuated repeatedly to remove oxygen; Agitation speed was set to 165 rpm.
- the oxygen free kettle was charged with 70 mmol fluorinated emulsifier (unless specified differently) as listed in table 3 and the following materials were added: 0.5 ml of a solution containing 40 mg of copper sulfate penta hydrate and 1 mg of conc.
- the ester was converted to the ammonium salt by saponification with aqueous ammonia and subsequent removal of methanol by distillation.
- a glass flask equipped with a reflux condenser, thermometer, and magnetic stirrer was used.
- Perfluoromethoxy propyl vinyl ether (498 g), t-butanol (149 g), water (1007 g), potassium hydroxide (280 g), and methyl trioctyl ammonium chloride (10 g) were added to the flask.
- the resulting two phase mixture was heated to reflux for 16 hours under vigorous stirring.
- the mixture was cooled to room temperature and sulfuric acid (588 g) was added.
- the two phase mixture was heated again under vigorous stirring. At about 70° C. gas began to evolve. Heating was continued until the gas evolution ceased.
- the reflux condenser was replaced by a distillation device which allowed the separation of a lower phase while returning the upper phase to the flask.
- Methanol 150 g was added and the mixture was heated for distillation. Distillation was carried out at ambient pressure without any intent for rectification. The condensed vapors separated into two phases. The lower phase was collected and the upper phase was returned to the flask. Distillation was continued until no more lower phase separated from the condensate.
- the combined crude ester (493 g) was purified by fractionated distillation, resulting in 401 g CF 3 O(CF 2 ) 3 OCHFCOOCH 3 with a boiling point of 51 to 52° C./22 mbar. This corresponds to a yield of 78%, based on vinyl ether used.
- the ester was converted to the ammonium salt by heating with aqueous ammonia and removal of methanol by fractionated distillation.
- a 2 liter glass flask equipped with a thermometer, reflux condenser, dropping funnel and stirrer was used. 674 g water, 136 g KMnO4, and 38 g NaOH are placed in the flask. 169 g C 3 F 7 OCHFCF 2 CH 2 OH were added to the well stirred mixture via the dropping funnel. The temperature is held below 50° C. Residual permanganate was destroyed by addition of a small amount of methanol. The resulting slurry was filtered to remove the MnO 2 . After washing the filter cake with water, the combined filtrate was transferred to a distillation apparatus and acidified with 65 g of sulfuric acid. 100 g methanol was added and a flash distillation was started.
- the ester was converted to the ammonium salt by saponification with aqueous ammonia and subsequent removal of methanol by distillation.
- a sample of diacid fluoride, FCOCF(CF 3 )—O—(CF 2 ) 5 COF (500 g, 1.1 mol) prepared from the hexafluoropropylene oxide (HFPO) coupling of perfluoroadipoyl fluoride as described in US Pub. No. US 2004/0116742 and was added over 2 hours to a stirred slurry of sodium carbonate (500 g, 4.7 mol) in 500 g of diglyme at 85° C. to make the disalt. The reaction liberated CO 2 gas. Distilled water (25 g, 1.4 mol) was added at 85° C. The mixture was heated up to 168° C. with CO 2 off-gassing and held for 30 minutes.
- HFPO hexafluoropropylene oxide
- the previous process was repeated two more times to yield a colorless acid.
- the surfactant CF 3 —CFH—O—(CF 2 ) 5 COONH 4 having a melting point of 159-165° C. was made quantitatively from the reaction of 200 g of acid reacted with excess ammonium hydroxide and dried.
- the surfactant CF 3 —CFH—O—(CF 2 ) 3 COONH 4 having a melting point of 64-68° C. was made quantitatively from the reaction of 208 g of acid reacted with excess ammonium hydroxide and dried.
- a mixture of 320 ml Tetrahydrofurane, 40 g Hydroxy acetic methylester and 188 g PPVE is cooled to 0° C., 27 g KOH-powder are added in small portions—during the addition of KOH, the reaction mixture heats up to 60° C. After the addition of KOH, the whole reaction mixture is agitated for 6 h at 25° C. The precipitated salt is separated by filtration, dissolved in 300 ml water and then treated with 57 g H 2 SO 4 (conc). The resulting mixture separates in two layers; the lower phase is C 3 F 7 —O—C 2 HF 3 —O—CH 2 —COOH, 86 g (56%). The distilled acid (bp. 125° C., 20 mbar) is neutralized with 25% aqueous ammonia solution to provide a 30% solution in water.
- a 2 liter glass flask equipped with a mechanical stirrer, thermometer and reflux condenser ( ⁇ 80° C.) is used. Heating of the flask is provided by an electric heating mantle. The conversion is carried out as a one pot reaction. 275 g perfluoropropyl vinyl ether (PPVE), 280 g KOH, 602 g water, 151 g t-butanol, and 10 g methyl trioctyl ammonium chloride are placed in the flask. The three phase mixture is subjected to vigorous stirring. After initial heating a moderate exothermic reaction occurs. Mixing is continued for nine hours. During this time the internal temperature adjusts to 27-33° C. Mixing is stopped when the exothermic reaction ceases.
- PPVE perfluoropropyl vinyl ether
- the reaction mixture forms two layers.
- the low temperature reflux condenser is replaced by a standard reflux condenser.
- Sulfuric acid (392 g) is slowly added without external cooling.
- the batch is heated to reflux. Unreacted PPVE is vented. At about 80° C. internal temperature gas begins to evolve. Heating is continued until the gas evolution has ceased. At this time the internal temperature reaches 101° C.
- the batch is cooled to RT and the reflux condenser is replaced by a distillation device. No column is used. 110 g methanol is added to the batch and distillation is started.
- the condensed vapors form two layers.
- the lower layer is separated and the upper layer is returned to the flask. Distillation is stopped when no more lower phase is formed. In total, 234 g of lower phase are collected. Fractionation of the lower phase yields 167 g of C 3 F 7 OCHFCOOCH 3 with a boiling point of 120-122° C. at ambient pressure.
- the calculated yield was 59% based on total PPVE used; 70% based on converted PPVE.
- the ester is converted to the ammonium salt by reaction with aqueous ammonia. Methanol is removed by fractionated distillation. The resulting aqueous solution is used as an emulsifier in the polymerization of fluorinated olefins.
- Oxidation of perfluorinated vinyl ethers with oxygen in the presence of SbF 5 was carried out as described in U.S. Pat. No. 4,987,254.
- the initially formed acid fluorides were esterified with methanol and purified by distillation.
- the distilled esters were converted to the corresponding ammonium salts by saponification with aqueous ammonia.
- a dry flask equipped with a magnetic stirrer bar, thermometer, dry ice reflux condenser, dropping funnel, and gas inlet tube was charged with 5 g of graphite.
- the flask was flushed with nitrogen and 332 g of CF 3 OCF 2 CF 2 CF 2 OCF ⁇ CF 2 were added at room temperature.
- CF 3 OCF 2 CF 2 COOCH 3 was isolated as a by-product. Saponification of the ester with aqueous ammonia at 60 to 80° C. and removal of methanol by distillation resulted in an aqueous solution of CF 3 OCF 2 CF 2 CF 2 OCF 2 COONH 4 . All structures were confirmed by 19 F-NMR spectra.
- Compound C-3 was synthesized by reaction of perfluorobutyric acid fluoride with tetrafluorooxethane and fluorination of the CH 2 group before conversion to the ammonium salts per WO 2005/003075.
- the perfluorinated and partially fluorinated carboxylates were evaluated for urinary clearance using a pharmacokinetic study in rats. The goal was to measure the total amount of parent compound eliminated via urinary output and estimate the rate of elimination. The study was approved by the IACUC (Institutional Animal Care and Use Committees) and was performed in 3M Company's AAALAC (Association for Assessment and Accreditation of Laboratory Animal Care )—accredited facility.
- the study utilized male Sprague Dawley rats, 6 to 8 weeks of age, and approximately 200 to 250 g body weight at study onset.
- the concentration of the parent compound or metabolites thereof were quantitatively measured via fluorine NMR on each urine sample for each animal at each time point based on internally added standards.
- T1 ⁇ 2 and % recovery are based on elimination of the major metabolite —C 3 F 7 —O—CHFCOO ⁇ .
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Abstract
Rf—O-L-CO2— (I)
Description
- This application claims priority to Great Britain Application No. 0525978.3, filed on Dec. 21, 2005; Great Britain Application No. 0523853.0, filed on Nov. 24, 2005; Great Britain Application No. 0514398.7, filed on Jul. 15, 2005; and Great Britain Application No. 0514387.0 filed on Jul. 15, 2005, all of which are herein incorporated by reference in their entirety.
- Fluoropolymers, i.e. polymers having a fluorinated backbone, have been long known and have been used in a variety of applications because of several desirable properties such as heat resistance, chemical resistance, weatherability, UV-stability etc. The various fluoropolymers are for example described in “Modern Fluoropolymers”, edited by John Scheirs, Wiley Science 1997. Commonly known or commercially employed fluoropolymers include polytetrafluoroethylene (PTFE), copolymers of tetrafluoroethylene (TFE) and hexafluoropropylene (HFP) (FEP polymers), perfluoroalkoxy copolymers (PFA), ethylene-tetrafluoroethylene (ETFE) copolymers, terpolymers of tetrafluoroethylene, hexafluoropropylene and vinylidene fluoride (THV) and polyvinylidene fluoride polymers (PVDF) and others. Commercially employed fluoropolymers include fluoroelastomers and thermoplastic fluoropolymers.
- Several methods are known to produce fluoropolymers. Such methods include suspension polymerization as disclosed in e.g. U.S. Pat. No. 3,855,191, U.S. Pat. No. 4,439,385 and EP 649863; aqueous: emulsion polymerization as disclosed in e.g. U.S. Pat. No. 3,635,926 and U.S. Pat. No. 4,262,101; solution polymerization as disclosed in U.S. Pat. No. 3,642,742, U.S. Pat. No. 4,588,796 and U.S. Pat. No. 5,663,255; polymerization using supercritical CO2 as disclosed in JP 46011031 and EP 964009 and polymerization in the gas phase as disclosed in U.S. Pat. No. 4,861,845.
- Currently, the most commonly employed polymerization methods include suspension polymerization and aqueous emulsion polymerization. Aqueous emulsion polymerization normally involves polymerization in the presence of a fluorinated surfactant. The suspension polymerization generally does not involve the use of surfactant but results in substantially larger polymer particles than in case of the aqueous emulsion polymerization. Thus, the polymer particles formed during suspension polymerization settle out of the reaction mixture whereas the dispersions obtained in emulsion polymerization generally exhibit good stability over a long period of time.
- An aqueous emulsion polymerization wherein no surfactant is used has been described in U.S. Pat. No. 5,453,477, WO 96/24622 and WO 97/17381 to generally produce homo- and copolymers of chlorotrifluoroethylene (CTFE). For example, WO 97/17381 discloses an aqueous emulsion polymerization in the absence of a surfactant wherein a radical initiator system of a reducing agent and oxidizing agent is used to initiate the polymerization and whereby the initiator system is added in one or more further charges during the polymerization. So-called emulsifier free polymerization has further been disclosed in WO 02/88206 and WO 02/88203. In the latter PCT application, the use of dimethyl ether or methyl tertiary butyl ether is taught to minimize formation of low molecular weight fractions that may be extractable from the fluoropolymer. WO 02/88207 teaches an emulsifier free polymerization using certain chain transfer agents to minimize formation of water-soluble fluorinated compounds. An emulsifier free polymerization is further disclosed in RU 2158274 for making an elastomeric copolymer of hexafluoropropylene and vinylidene fluoride.
- Notwithstanding the fact that emulsifier free polymerizations are known, the aqueous emulsion polymerization process in the presence of fluorinated surfactants is still a desirable process to produce fluoropolymers because it can yield stable fluoropolymer particle dispersions in high yield and in a more environmental friendly way than for example polymerizations conducted in an organic solvent. Frequently, the emulsion polymerization process is carried out using a perfluoroalkanoic acid or salt thereof as a surfactant. These surfactants are typically used because they provide a wide variety of desirable properties such as high speed of polymerization, good copolymerization properties of fluorinated olefins with comonomers, small particle sizes of the resulting dispersion, desirable stability, and good polymerization yields, i.e. a high amount of solids can be produced. However, environmental concerns have been raised against these surfactants and moreover these surfactants are generally expensive. In particular, perfluorinated alkanoic acids having 8 or more carbon atoms are known to be bio-accumulating.
- Alternative surfactants to the perfluoroalkanoic acids or salts thereof have also been proposed in the art for conducting the emulsion polymerization of fluorinated monomers.
- For example, surfactants of the general formula Rf—C2H4—SO3M, wherein Rf represents a perfluorinated aliphatic group and wherein M represents a cation, have been disclosed in U.S. Pat. No. 5,789,508, U.S. Pat. No. 4,025,709, U.S. Pat. No. 5,688,884 and U.S. Pat. No. 4,380,618.
- U.S. Pat. No. 5,763,552 discloses partially fluorinated surfactants of the general formula Rf—(CH2)m—R′f—COOM wherein Rf represents a perfluoroalkyl group or a perfluoroalkoxy group of 3 to 8 carbon atoms, R′f represents a perfluoroalkylene of 1 to 4 carbon atoms and m is 1-3.
- U.S. Pat. No. 4,621,116 discloses perfluoroalkoxy benzene sulfonic acids and salts thereof in the aqueous emulsion polymerization of fluorinated monomers.
- U.S. Pat. No. 3,271,341 teaches perfluoropolyethers of the general formula:
-
F—(CF2)m—O—[CFX—CF2—O]n—CFX—COOA - wherein m is 1 to 5, X is F or CF3, A is a monovalent cation and n is 0 to 10. The perfluoropolyethers are taught as emulsifiers in the emulsion polymerization of ethylenically unsaturated monomers.
- US 2005/0090613 discloses fluorinated polyethers of the formula:
-
F—(CF2)m—O—[CFX—CF2—O]n—CFX—COOA - wherein m is 3 to 10, X is F or a perfluoroalkyl group, n is 0, 1 or 2 and A is the counter ion of the carboxylic anion. These polyethers are taught as emulsifiers in the emulsion polymerization of fluorinated olefins.
- The use of perfluoropolyethers having neutral end groups in an aqueous emulsion polymerization is disclosed in U.S. Pat. No. 4,864,006, U.S. Pat. No. 4,789,717 and EP 625526. For example U.S. Pat. No. 4,864,006 and EP 625526 disclose the use of microemulsion prepared from perfluoropolyethers having neutral end groups in an aqueous emulsion polymerization of fluorinated monomers. In a particular embodiment, a certain perfluoropolyether having carboxylic end groups is taught to emulsify the neutral perfluoropolyether.
- EP 1,334,996 discloses certain perfluoropolyethers having carboxylic acid groups or salts thereof at both end groups, i.e. the perfluoropolyethers are bifunctional. The perfluoropolyethers are taught for use in aqueous dispersions of fluoropolymers and in the preparation of such dispersion by aqueous emulsion polymerization.
- WO 00/71590 teaches the use of a combination of perfluoropolyether surfactants having a carboxylic acid group or salt thereof with a fluoroalkyl carboxylic acid or sulfonic acid or salt thereof. It is taught that the perfluoropolyether surfactants on their own are not very powerful surfactants.
- Still further fluorinated ether surfactants for emulsion polymerization have been described in WO 05/03075.
- In WO 05/121290, JP 73-03278, U.S. Pat. No. 3,882,153 oligomers from VDF are disclosed for emulsion polymerization.
- In one aspect, the present invention relates to a process comprising polymerizing tetrafluoroethylene in an aqueous emulsion in the presence of a non-telogenic surfactant having an anionic portion with the general formula (I):
-
Rf—O-L-CO2— (I) - wherein Rf is selected from a partially fluorinated alkyl group, a perfluorinated alkyl group, a partially fluorinated alkyl group interrupted by one or more oxygen atoms, and a perfluorinated alkyl group interrupted by one or more oxygen atoms, wherein Rf has from 1 to 10 carbon atoms; and L is an alkylene group having the general formula (CX2)n wherein each X is independently selected from Rf, fluorine, and hydrogen and n is selected from1 to 5, with the proviso that the surfactant contains at least one unit selected from a —CH2— unit and a —CHF—— unit.
- In another aspect, the present invention relates to an aqueous dispersion of a tetrafluoroethylene-containing perfluoropolymer comprising a non-telogenic surfactant having an anionic portion with the general formula:
-
Rf—O-L-CO2— - wherein Rf is selected from a partially fluorinated alkyl group, a perfluorinated alkyl group, a partially fluorinated alkyl group interrupted by one or more oxygen atoms, and a perfluorinated alkyl group interrupted by one or more oxygen atoms, wherein Rf has from 1 to 10 carbon atoms; and L is an alkylene group having the general formula (CX2)n wherein each X is independently selected from Rf, fluorine, and hydrogen and n is selected from 1 to 5, with the proviso that the surfactant contains at least one unit selected from a —CH2— unit and a —CHF— unit.
- In another aspect, the invention relates to processes to prevent or at least reduce explosions in the production of polytetrafluoroethylene and other perfluoropolymers.
- In the present application, when the term is used “interrupted with one or more oxygen atoms”, it is meant that one or more ether groups may be present in the aliphatic group. That is, for instance, where two oxygen atoms are present, they are separated by at least one carbon atom, so as to form a di-ether. Peroxide structures are not contemplated by the term “interrupted by one or more oxygen atoms”.
- The present inventors recognize the desirability of finding an alternative emulsion polymerization process in which the use of perfluoroalkanoic acids and salts thereof as a fluorinated surfactant can be avoided or at least greatly reduced. In particular, it would be desirable to find an alternative surfactant or dispersant, in particular one that for example has a low toxicity and/or shows no or only little bioaccumulation. It would also be desirable that the alternative surfactant has good chemical and thermal stability enabling polymerization over a wide range of conditions of for example temperature and/or pressure.
- In some embodiments, the alternative surfactant or dispersant allows for a high polymerization rate, good dispersion stability, good yields, good copolymerization properties and/or the possibility of obtaining a wide variety of particle sizes including small particle sizes. The properties of the resulting fluoropolymer should generally not be negatively influenced and preferably would be improved.
- In other embodiments, the resulting dispersions, concentrated dispersions, and fluoropolymers obtainable from dispersions as described herein, have good or excellent properties in coating applications and/or impregnation of substrates, including for example good film forming properties.
- It would further be desirable that the polymerization can be carried out in a convenient and cost effective way, preferably using equipment commonly used in the aqueous emulsion polymerization of fluorinated monomers. Additionally, it may be desirable to recover the alternative surfactant or dispersant from wastewater streams and/or to remove or recover the surfactant from the dispersion subsequent to the polymerization. Desirably, such recovery can proceed in an easy, convenient and cost effective way. Recovery processes have been reviewed in EP 1514848 and a particular method involves treating the aqueous liquid with adsorbent particles including for example an anion exchange resin as disclosed in EP 1083441, EP 1084097 or other adsorbent particles such as activated carbon particles as disclosed in WO 2005/082785. The processes are typically practiced for recovering perfluorooctanoic acid or salts thereof, which is the most widely used surfactant in making fluoropolymers through aqueous emulsion polymerization. These processes can be adapted to recover the surfactants described herein, having an anionic portion with general formula (I).
- The present invention provides a process comprising polymerizing tetrafluoroethylene in an aqueous emulsion in the presence of a non-telogenic surfactant having an anionic portion with the general formula (I):
-
Rf—O-L-CO2— (I) - wherein Rf is selected from a partially fluorinated alkyl group, a perfluorinated alkyl group, a partially fluorinated alkyl group interrupted by one or more oxygen atoms, and a perfluorinated alkyl group interrupted by one or more oxygen atoms, wherein Rf has from 1 to 10 carbon atoms; and L is an alkylene group having the general formula (CX2)n wherein each X is independently selected from Rf, fluorine, and hydrogen and n is selected from 1 to 5, with the proviso that the surfactant contains at least one unit selected from a —CH2— unit and a —CHF— unit. The invention pertains to a safe technology for the production of perfluoropolymers (e.g. PTFE) through aqueous emulsion polymerization of TFE, whereby a significant cause of explosion is avoided.
- Without wishing to be bound by theory and without admitting that such is the case, it is believed that the following explanation for the surprising discovery can be made:
- TFE is thermodynamically unstable, and decomposes with great reaction enthalpy into carbon and tetrafluoromethane. Under adiabatic and isochoric conditions, the initial pressure increases by 8- to 10-fold during the decomposition.
- The decomposition, however, requires an ignition temperature of about 300° C. The invention is based on the knowledge that the explosions start from so-called “hot spots”. The “hot spots” form from small amounts of floating fluoropolymer dispersion coagulate. The tetrafluoroethylene polymer coagulate floats on the aqueous surface of the polymerization media, despite having a density of more than 2 g/cm3. Under these conditions, the coagulate is exposed to an elevated TFE concentration in the gas phase, which causes the polymerization speed to accelerate at the polymer-monomer interface. Concurrently, the cooling at the surface is decreased due to the lack of heat transfer fluid (water). These effects combined lead to a heating of the coagulate above the ignition temperature of TFE, which is approximately 300° C. In conjunction with the heating, lumps can form in which for example the PTFE is not only melted, but is also black in color (carbonized). Melted PTFE and carbonized PTFE have been found in polymerization product following explosions. Temperatures above approximately 450° C. are required for carbonization of PTFE.
- One attribute of TFE polymerization is that the polymer chain radicals cannot terminate themselves because there is no chain transfer of the polymer in which a fluorine atom separates in order to form a terminal double bond. Consequently, the heat-generating radicals are fixed in place within the coagulate surfaces.
- It has been found that in other processes in which the fluorinated radicals can terminate by means of a radical transfer reaction, “hot spots” do not occur, nor have explosions been observed. As a result, in accordance with the processes described herein, an emulsifier is added to the aqueous phase of the polymerization kettle which is capable of sufficiently quickly carrying away the locus of polymerization from floating coagulate via radical transfer. As a result, the ignition temperature is not reached in the floating coagulate.
- The non-telogenic surfactants having the anionic portion with general formula (I), described above, do not show significant telogenic activities under standard polymerization conditions for making PTFE. By standard polymerization conditions is meant at a temperature range of from 0 to 150, for instance from about 10 to 100° C., and at a partial pressure of tetrafluoroethylene of from 2 to 40 bar, for instance, from 5 to 30 bar. Only at very high temperatures, for instance, beyond 300° C., does the non-telogenic surfactant act as chain transfer agent. The concentration for the surfactants is typically from 0.005 to 1% by weight based on the amount of fluoropolymer solids in the aqueous dispersion.
- Because the aqueous emulsion polymerization described herein can be carried out without the need for using a perfluoroalkanoic acid, dispersions can be readily obtained that are free of perfluoroalkanoic acids or salts thereof. Thus, in some embodiments, the present invention provides aqueous dispersions of a fluoropolymer comprising a surfactant of formula (I) as the only emulsifier in the composition.
- The resulting dispersions can be used in a variety of applications including coating and impregnation of substrates. Generally, a non-ionic surfactant should be added to the dispersion for such applications. Accordingly, the invention in a further aspect relates to aqueous dispersions of a fluoropolymer comprising a surfactant of formula (I) as an emulsifier and additionally comprising a non-ionic surfactant. The non-ionic surfactant is typically present in an amount of from 1 to 12% by weight based on the weight of fluoropolymer solids.
- The aqueous emulsion polymerization of fluorinated monomers, including gaseous fluorinated monomers, can be conducted using one or more surfactants according to formula (I) as an emulsifier. In one particular embodiment, the polymerization may be carried out using a mixture of surfactants of formula (I).
- Particular examples of linking groups L may be selected from the following:
- —(CF2)g— wherein g is 1, 2, 3, 4, 5 or 6;
- —CFH—(CF2)h— wherein h is 0, 1, 2, 3, 4 or 5;
- —CF2—CFH—(CF2)d— wherein d is 0, 1, 2, 3 or 4;
- —CH2—(CF2)h— wherein h is 1, 2, 3 or 4;
- —(CH2)c— wherein c is 1.
- Examples of surfactants according to formula (I) are those having anionic portions of the following formulae:
-
CF3—CHF—O—(CF2)a—CO2—, wherein a is selected from 1 to 5; - Rf′—O—CHF—CO2—, wherein Rf′ is selected from a perfluorinated alkyl group having from 1 to 10 carbon atoms and a perfluorinated alkyl group interrupted by one or more oxygen atoms and having from 1 to 10 carbon atoms;
- Rf′—O—CHF—CF2—CO2—, wherein Rf′ is selected from a perfluorinated alkyl group having from 1 to 10 carbon atoms and a perfluorinated alkyl group interrupted by one or more oxygen atoms and having from 1 to 10 carbon atoms;
- Rf′—O—CF2—CHF—CO2—, wherein Rf′ is selected from a perfluorinated alkyl group having from 1 to 10 carbon atoms and a perfluorinated alkyl group interrupted by one or more oxygen atoms and having from 1 to 10 carbon atoms;
- Rf′—O—CF2CHFCF2CO2— wherein Rf′ is selected from a perfluorinated alkyl group having from 1 to 10 carbon atoms and a perfluorinated alkyl group interrupted by one or more oxygen atoms and having from 1 to 10 carbon atoms;
- and combinations thereof.
- Specific examples of the surfactants described herein include:
-
Rf—O—CHF—COOH -
C3F7—O—CHF—COOH -
CF3—O—CF2CF2—CF2—O—CHF—COOH -
CF3CF2CF2 —O—CF2CF2—CF2—O—CHF—COOH -
CF3—O—CF2—CF2—O—CHF—COOH -
CF3—O—CF2—O—CF2—CF2—O—CHF—COOH -
CF3—(O—CF2)2—O— CF2—CF2—O—CHF—COOH -
CF3—(O—CF2)3—O— CF2—CF2—O—CHF—COOH -
Rf—O—CHF—CF2—COOH -
CF3—O—CHF—CF2—COOH -
CF3—O—CF2—CF2—O—CHF—CF2—COOH -
CF3—CF2—O—CHF—CF2—COOH -
CF3—O—CF2—CF2—CF2—O—CHF—CF2—COOH -
CF3—O—CF2—O— CF2—CF2—O—CHF—CF2—COOH -
CF3—(O—CF2)2—O— CF2—CF2—O—CHF—CF2—COOH -
CF3—(O—CF2)3—O— CF2—CF2—O—CHF—CF2—COOH -
Rf—O—CF2—CHFCOOH -
CF3—O—CF2—CHF—COOH -
C3F7—O—CF2—CHF—COOH -
CF3—O—CF2—CF2—CF2—O—CF2—CHF—COOH -
CF3—O—CF2—O—CF2—CF2—O—CF2—CHF—COOH -
CF3—(O—CF2)2—O—CF2—CF2—O—CF2—CHF—COOH -
CF3—(O—CF2)3—O—CF2—CF2—O—CF2—CHF—COOH -
Rf—O—CF2—CHF—CF2COOH -
CF3—O—CF2—CHF—CF2—COOH -
C2F5—O—CF2—CHF—CF2—COOH -
C3F7—O—CF2—CHF—CF2—COOH -
CF3—O—CF2—CF2—CF2—O—CF2—CHF—CF2—COOH -
CF3—O—CF2—O— CF2—CF2—O—CF2—CHF—CF2—COOH -
CF3—(O—CF2)2—O— CF2—CF2—O—CF2—CHF—CF2—COOH -
CF3—(O—CF2)3—O—CF2—CF2—O—CF2—CHF—CF2—COOH -
Rf—(O)m—CHF—CF2—O—CH2—COOH m=0 or 1 -
CF3—O—CHF—CF2—O—CH2—COOH -
CF3—O—CF2—CF2—CF2—O—CHF—CF2—O—CH2—COOH -
C3F7—O—CHF—CF2—O—CH2—COOH -
C3F7—O—CF2—CF2—O—CHF—CF2—OCH2COOH -
C3F7—O—CF2—CF2—CF2—O—CHF—CF2—OCH2COOH -
C3F7—O—CF2—CHF—CF2—OCH2COOH -
CF3—CHF—CF2—O—CH2COOH -
C3F7—CF2—CHF—CF2—OCH2—COOH -
Rf—O—((CF2)n—O)m—CH2—COOH n=1, 2, or 3; m=0, 1, 2 -
CF3—O—CF2—CF2—O—CH2—COOH -
CF3—O—CF2—CF2—CF2—O—CF2—CF2—O—CH2—COOH -
C3F7—O—CF2—CF2—O—CH2—COOH -
C3F7—O—CF2—CF2—O—CF2—CF2—OCH2COOH -
C3F7—O— CF2—CF2—CF2—O—CF2—CF2—OCH2COOH -
C3F7—O—CF2—CF2—CF2—OCH2COOH -
C4F9—O—CH2—COOH -
C3F7— O—CH2COOH -
C6F13—OCH2—COOH -
CF3 CHF—O—(CF2)o—COOH with o being an integer of 1, 2, 3, 4, 5 or 6 -
CF3CFH—O—(CF2)3—COOH -
CF3CFH—O—(CF2)5—COOH - In accordance with the present invention, the surfactant is used in the aqueous emulsion polymerization of tetrafluoroethylene, either as a homopolymer to give polytetrafluoroethylene, as a copolymer with perfluorovinyl ethers (PFA, MFA), or as a copolymer with hexafluoropropylene (FEP). Polymerizing tetrafluoroethylene yields a polytetrafluoroethylene (PTFE) that is high in molecular weight and correspondingly has an SSG density (ASTM D 4895-04) of less than 2.25 g/cm3 (inclusive) and is non melt-processable.
- As used herein, the term “non-telogenic surfactant” refers to a surfactant in the presence of which it is possible to obtain a non-melt processable PTFE having an SSG density (ASTM D 4895-04) of less than 2.25 g/cm3 (inclusive). In some embodiments a PTFE can be prepared with an SSG density of less than 2.20, even less than 2.19, 2.17, or even lower. In other words, the surfactants described herein allow for the preparation of PTFE having an SSG density comparable to those PTFE's prepared in the presence of perfluorooctanoic acid.
- Other copolymers of tetrafluoroethylene are also contemplated by the present invention. These copolymers may include, in addition to tetrafluoroethylene, one or more fluorinated monomers, in particular gaseous fluorinated monomers. By gaseous fluorinated monomers is meant monomers that are present as a gas under the polymerization conditions.
- In a particular embodiment, the polymerization of the tetrafluoroethylene, optionally in the presence of one or more additional fluorinated monomers is initiated in the presence of the surfactant of formula (I), for instance, in an aqueous emulsion polymerization. The amount of surfactant of formula (I) may vary depending on the desired properties of the resulting aqueous dispersion, such as the amount of solids, the fluoropolymer particle size, and the like. Generally, the amount of surfactant of formula (I) will be from 0.005% by weight based on the weight of fluoropolymer solids in the aqueous emulsion to 1% by weight; for example, from 0.01% by weight and 0.75% by weight. Some embodiments have a range of from 0.1% by weight to 0.5% by weight.
- The anionic portion of the partially fluorintated carboxylic acid used in the process of the invention corresponds to formula (I). Generally, the fluorinated carboxylic acid anion will be a low molecular weight compound, for example a compound having a molecular weight of not more than 1000 g/mol, typically not more than 600 g/mol and in particular embodiments, the fluorinated carboxylic acid anion may have a molecular weight of not more than 500 g/mol.
- While the polymerization may be initiated in the presence of the surfactant of formula (I), it is also contemplated that the surfactant of formula (I) is added during the polymerization.
- It may, for instance, be desirable to add certain monomers to the polymerization in the form of an aqueous emulsion. For example, fluorinated monomers and in particular perfluorinated co-monomers that are liquid under the polymerization conditions may be added to the polymerization in the form of an aqueous emulsion of the monomer. Such emulsions may be prepared using the surfactant of formula (I) or by using a different surfactant. The emulsions of monomer prepared and added to the polymerization may be in the form of a micro-emulsion.
- The aqueous emulsion polymerization may be carried out at a temperature of from 0 to 150° C. For instance, the temperature may be from 10° C. and higher, from 20° C. and higher, even from 30° C. and higher. The temperature may be up to 100° C., up to 90° C., even up to 80° C. The partial pressure of tetrafluoroethylene in the headspace of the reactor is typically from 5 to 30 bar, in particular, from 5 to 20 bar. The reaction temperature may be varied during the polymerization to influence the molecular weight distribution, e.g., to obtain a narrow or broad molecular weight distribution or to obtain a bimodal or multimodal molecular weight distribution.
- The aqueous emulsion polymerization is typically initiated by an initiator including any of the initiators known for initiating a free radical polymerization of fluorinated monomers. Suitable initiators include peroxides and azo compounds and redox based initiators. Specific examples of peroxide initiators include, hydrogen peroxide, sodium or barium peroxide, diacylperoxides such as diacetylperoxide, disuccinoyl peroxide, dipropionylperoxide, dibutyrylperoxide, diglutaric acid peroxide, and further per-acids and salts thereof such as e.g. ammonium, sodium or potassium salts. Examples of per-acids include peracetic acid. Esters of the peracid can be used as well. Examples of inorganic initiators include for example ammonium- alkali- or earth alkali salts of persulfates, permanganic or manganic acid or manganic acids.
- A persulfate initiator, e.g. ammonium persulfate (APS), may be used alone or may be used in combination with a reducing agent. Suitable reducing agents include bisulfites such as for example ammonium bisulfite or sodium metabisulfite, thiosulfates such as for example ammonium, potassium or sodium thiosulfate, hydrazines, azodicarboxylates and azodicarboxyldiamide (ADA). Further reducing agents that may be used include sodium formaldehyde sulfoxylate (Rongalit®, available from BASF, Germany) or fluoroalkyl sulfinates. The reducing agent typically reduces the half-life time of the persulfate initiator. Additionally, a metal salt catalyst such as for example copper, iron or silver salts may be added.
- The amount of initiator may be from 0.0001% by weight (based on the fluoropolymer solids to be produced) to 1% by weight. In one embodiment, the amount of initiator is from 0.0005 to 0.5% by weight. In another embodiment, the amount may be from 0.005 to 0.3% by weight.
- The aqueous emulsion polymerization system may further comprise other materials, such as buffers and, if desired, complex-formers or chain-transfer agents. When present, chain transfer agents are typically present in small amounts so as to not interfere with the preparation of high molecular weight polymers. Examples of chain transfer agents that can be used include ethers, such as dimethyl ether, and methyl t-butyl ether; alkanes having 1 to 5 carbon atoms such as ethane, propane and n-pentane; halogenated hydrocarbons such as CCl4, CHCl3 and CH2Cl2 and hydrofluorocarbon compounds; and alcohols.
- Other compounds that may be present during the polymerization, which may or may not act as a chain transfer agent, include organic, saturated, hydrogen—containing fluorinated compounds that have a water solubility at 25° C. of from 1×10−3 (mol/l*bar) to 4×10−3 (mol/l*bar). Such compounds may be useful in suppressing explosions by providing supplemental quenching of “hot spots”. Such fluorinated compounds are typically present at a partial pressure of from 2.5 mbar to 0.5 bar. These compounds may, in some embodiments, be partially fluorinated hydrocarbons that contain chlorine or ether bridges. In other embodiments, the fluorinated compounds contain at least one —CH2— group or at least one —CH3 group. In yet further embodiments, the fluorinated compounds are selected from 1,1,1-trifluoroethane, 1,1,2-trifluoroethane, 1,1,1,2-tetrafluoroethane, and combinations thereof.
- Although the present invention is best suited for the TFE—homopolymerization, and in particular for making high molecular weight PTFE as well as modified PTFE, it is also applicable to other perfluorinated copolymers as described herein.
- Examples of fluorinated monomers that may be polymerized using the surfactant of formula (I) as an emulsifier include fully fluorinated gaseous monomers including fluorinated olefins such as tetrafluoroethylene, chlorotrifluoroethylene, hexafluoropropylene, fully fluorinated allyl ethers and fully fluorinated vinyl ethers.
- Further examples of fluorinated monomers that may be used in the aqueous emulsion polymerization according to the invention include those corresponding to the formula:
-
CF2═CF—O—Rf (II) - wherein Rf in formula (II) represents a perfluorinated aliphatic group that may contain one or more oxygen atoms. Preferably, the perfluorovinyl ethers of formula (II) correspond to the general formula:
-
CF2═CFO(RfO)n(R′fO)mR″f (III) - wherein Rf and R′f in formula (III) are different linear or branched perfluoroalkylene groups of from 2 to 6 carbon atoms, m and n are each independently from 0 to 10, and R″f is a perfluoroalkyl group of from 1 to 6 carbon atoms. Examples of perfluorovinyl ethers according to the above formulas (II) and (III) include perfluoro-2-propoxypropylvinyl ether (PPVE-2), perfluoro-3-methoxy-n-propylvinyl ether, perfluoro-2-methoxy-ethylvinyl ether, perfluoromethylvinyl ether (PMVE), perfluoroethylvinyl ether (PEVE), perfluoropropylvinyl ether (PPVE), perfluoro-n-propylvinyl ether (PPVE-1) and CF3—(CF2)2—O—CF(CF3)—CF2—O—CF(CF3)—CF2—O—CF═CF2.
- The aqueous emulsion polymerization may be used to produce a variety of fluoropolymers including perfluoropolymers. Also the aqueous emulsion polymerization may result in melt—processable fluoropolymers as well as those that are not melt-processable. Obtainable polymers include, for example, polytetrafluoroethylene and so-called modified polytetrafluoroethylene.
- The aqueous emulsion polymerization results in a dispersion of the fluoropolymer in water. Generally, the amount of solids of the fluoropolymer in the dispersion directly resulting from the polymerization will vary from 3% by weight to 40% by weight, depending on the polymerization conditions. A typical range is from 5 to 35%, for instance, from 10 to 30% by weight.
- The particle size (volume average particle size) of the fluoropolymer may be from 50 nm to 350 nm, with a typical particle size being from 100 nm to 300 nm.
- The amount of surfactant having an anionic portion with the general formula (I) in the resulting dispersion is typically from 0.005 to 1% by weight based on the weight of fluoropolymer solids in the aqueous dispersion. A typical amount may be from 0.01 to 0.75% by weight or from 0.1 to 0.5% by weight, based on the weight of the fluoropolymer solids.
- The fluoropolymer may be isolated from the dispersion by coagulation if a polymer in solid form is desired. Also, depending on the requirements of the application in which the fluoropolymer is to be used, the fluoropolymer may be post-fluorinated so as to convert any thermally unstable end groups into stable CF3 end groups. Generally, when the fluoropolymer is post fluorinated, it is post fluorinated such that the amount of end groups in the fluoropolymer other than CF3 is less than 80 per million carbon atoms.
- For coating applications, an aqueous dispersion of the fluoropolymer may be desired and hence the fluoropolymer may not need to be separated or coagulated from the dispersion. To obtain a fluoropolymer dispersion for use in coating applications such as, for example, in the impregnation of fabrics or in the coating of metal substrates to make for example cookware, further stabilizing surfactants may be added and/or the level of fluoropolymer solids may be increased. For example, non—ionic stabilizing surfactants may be added to the fluoropolymer dispersion. Typically these will be added to an aqueous fluoropolymer dispersion in an amount of 1 to 12% by weight based on fluoropolymer solids. Examples of non-ionic surfactants that may be added include
-
R1—O—[CH2CH2O]n—[R2O]m—R3 (V) - wherein R1 represents an aromatic or aliphatic hydrocarbon group (linear or branched) having at least 8 carbon atoms, R2 represents an alkylene having 3 carbon atoms, R3 represents hydrogen or a C1-C3 alkyl group, n has a value of 0 to 40, m has a value of 0 to 40 and the sum of n+m being at least 2. It will be understood that in the above formula (V), the units indexed by n and m may appear as blocks or they may be present in an alternating or random configuration. Examples of non—ionic surfactants according to formula (V) above include alkylphenol ethoxylates such as ethoxylated p-isooctylphenol commercially available under the brand name TRITON™ such as for example TRITON™ X100 wherein the number of ethoxy units is about 10 or TRITON™ X114 (available from Dow Chemical, Midland, Mich.) wherein the number of ethoxy units is about 7 to 8. Still further examples include those in which R1 in the above formula (V) represents an alkyl group of 4 to 20 carbon atoms, m is 0 and R3 is hydrogen. An example thereof includes isotridecanol ethoxylated with about 8 ethoxy groups and which is commercially available as GENAPOL®X080 (available from Clariant GmbH, Germany). Non-ionic surfactants according to formula (V) in which the hydrophilic part comprises a block-copolymer of ethoxy groups and propoxy groups may be used as well. Such non-ionic surfactants are commercially available from Clariant GmbH under the trade designation GENAPOL®PF 40 and GENAPOL®PF 80.
- The amount of fluoropolymer solids in the dispersion may be up-concentrated as needed or desired to an amount between 30 and 70% by weight. Any of the known up-concentration techniques may be used including ultra-filtration and thermal up-concentration.
- In some embodiments the surfactant may be removed or reduced from fluoropolymer dispersions described herein. The methods for removal include those generally known in the art including those described in U.S. Pat. No. 6,833,403, Blädel, et al.
- Applications for the fluoropolymers and fluoropolymer dispersions made from the processes described herein include those commonly known for fluoropolymers. These applications include, for instance, those described in “Fluoroplastics: Vol. 1, Non-Melt Processible Fluoroplastics”, Ebnesajjad, Chapter 17 (2000).
- The inventors have also found that the reduced risk of explosion associated with polymerization processes carried out as described herein allows for polymerization on a commercial scale to be carried out in larger reactors and at higher solids content than is safely achieved under previously employed polymerization processes.
- Advantages and embodiments of this invention are further illustrated by the following examples, but the particular materials and amounts thereof recited in these examples, as well as other conditions and details, should not be construed to unduly limit this invention. All parts and percentages are by weight unless otherwise indicated.
- The latex particle size determination was conducted by means of dynamic light scattering with a Malvern Zetasizer 1000 HAS in accordance to ISO/DIS 13321. Prior to the measurements, the polymer latexes as yielded from the polymerizations were diluted with 0.001 mol/L KCl-solution, the measurement temperature was 25° C. in all cases. The reported average is the Z-average particle diameter.
- SSG: Standard specific gravity was measured according ASTM 4895-04
- Solid Content: Determination of solid content was done by subjecting the latex sample to a temperature up to 250° C. for 30 min.
- The polymerization experiments were performed in a 40 l kettle equipped with an impeller agitator and a baffle. The kettle was charged with 30 l of deionized water and set to 35° C.; the kettle was evacuated repeatedly to remove oxygen; Agitation speed was set to 165 rpm. The oxygen free kettle was charged with 70 mmol fluorinated emulsifier (unless specified differently) as listed in table 3 and the following materials were added: 0.5 ml of a solution containing 40 mg of copper sulfate penta hydrate and 1 mg of conc. sulfuric acid; 15 g of a 25 w- % of aqueous ammonia solution and 5.6 g of CF3CF2CF2—O—CF(CF3)—CF2-O—CF═CF2 (PPVE-2). Finally the reactor was pressurized with tetrafluoroethylene (TFE) to 0.2 MPa and 47 g of hexafluoropropylene (HFP) were added. The kettle was then set to 1.5 MPa using TFE and 100 ml of an aqueous initiator solution containing 140 mg of sodium disulfite followed by 100 ml of a solution containing 340 mg of ammonium peroxodisulfate was pumped into the reactor. The beginning of the polymerization is indicated by a pressure drop. During polymerization the pressure was maintained at 1.5 MPa by feeding TFE continuously. After 3.2 kg of TFE had been added, the monomer valve was closed and the pressure was released. The characteristics of the obtained polymer latexes are summarized in table 3.
- 1000 ml of this polymer dispersion were coagulated by adding 20 ml hydrochloric acid under agitation. The coagulated material was agglomerated with gasoline and washed repeatedly. The agglomerated polymer was dried overnight at 200° C. in a vacuum oven; test data are given in table 3.
-
TABLE 1 Emulsifier Example C7F15COONH4 Comparative example C-1 CF3—O—(CF2)3—O—CF2—COONH4 Comparative compound C-2 C4F9—O—CF2—CF2—COONH4 Comparative compound C-3 CF3—O—CF2—CF2—CF2—O—CHF—CF2—COONH4 Compound 1 CF3—O—CF2—CF2—CF2—O—CHF—COONH4 Compound 2 C3F7—O—CFH—CF2COONH4 Compound 3 CF3—CFH—O—(CF2)5—COONH4 Compound 4 CF3—CFH—O—(CF2)3—COONH4 Compound 5 C3F7—O—CFH—CF2—O—CH2—COONH4 Compound 6 C3F7—O—CFH—COONH4 Compound 7 - a. Preparation of CF3O(CF2)3OCHFCF2CH2OH
- Using equipment similar to the described above, 255 g of perfluoromethoxypropyl vinyl ether and 730 g methanol were converted with Rongalit and t-butylhydroperoxide as radical source. Reaction temperature started at 47° C. and reached 64° C. at the end. Work up by distillation yielded 166 g of pure CF3O(CF2)3OCHFCF2CH2OH with a boiling point of 60-61° C./20 mbar. This corresponds to a yield of 59%.
- b. Preparation of CF3O(CF2)3OCHFCF2COONH4
- A 2 liter glass flask equipped with a thermometer, reflux condenser, dropping funnel and stirrer was used. 159 g of CF3O(CF2)3OCHFCF2CH2OH, 520 g water, and 100 g sulfuric acid were added to the flask. 190 g KMnO4 were added manually to the liquid over a period of 2 hours while stirring. The reaction temperature increased to 95° C. over time. After a post reaction time of two hours, an aqueous solution of sodium bisulfite was added until a clear solution was formed. 100 g of methanol and in total 400 g of 50% aqueous sulfuric acid were added. Flash distillation of the reaction mixture resulted in a two phase distillate. Fractionation of the lower phase (120 g) gave 85.5 g of CF3O(CF2)3OCHFCF2COOCH3 (bp 34-35° C./6 mbar; yield 50%).
- The ester was converted to the ammonium salt by saponification with aqueous ammonia and subsequent removal of methanol by distillation.
- A glass flask equipped with a reflux condenser, thermometer, and magnetic stirrer was used. Perfluoromethoxy propyl vinyl ether (498 g), t-butanol (149 g), water (1007 g), potassium hydroxide (280 g), and methyl trioctyl ammonium chloride (10 g) were added to the flask. The resulting two phase mixture was heated to reflux for 16 hours under vigorous stirring. The mixture was cooled to room temperature and sulfuric acid (588 g) was added. The two phase mixture was heated again under vigorous stirring. At about 70° C. gas began to evolve. Heating was continued until the gas evolution ceased. The reflux condenser was replaced by a distillation device which allowed the separation of a lower phase while returning the upper phase to the flask. Methanol (150 g) was added and the mixture was heated for distillation. Distillation was carried out at ambient pressure without any intent for rectification. The condensed vapors separated into two phases. The lower phase was collected and the upper phase was returned to the flask. Distillation was continued until no more lower phase separated from the condensate. The combined crude ester (493 g) was purified by fractionated distillation, resulting in 401 g CF3O(CF2)3OCHFCOOCH3 with a boiling point of 51 to 52° C./22 mbar. This corresponds to a yield of 78%, based on vinyl ether used. The ester was converted to the ammonium salt by heating with aqueous ammonia and removal of methanol by fractionated distillation.
- Alternatively, the previous reaction was repeated but 36 g of an aqueous solution containing 11 g of CF3O(CF2)3OCHFCOONH4 was used as phase transfer catalyst instead of methyl trioctyl ammonium chloride. The mixture was slowly heated to 70° C. internal temperature. Total reaction time was 26 hours. Work up was carried out as described above. 438 g of distilled CF3O(CF2)3OCHFCOOCH3 was received. This corresponds to a yield of 83% (calculation includes the amount of phase transfer catalyst).
- The conversion to the ammonium salt was carried out as above.
- a. Preparation of CF3CF2CF2OCHFCF2CH2OH
- In a 2 liter glass flask equipped with a stirrer, thermometer, reflux condenser, and dropping funnel were placed 1008 g methanol, 266 g perfluoropropyl vinyl ether, and 9.2 g of Rongalit® (sodium hydroxymethyl sulfinate). The reaction mixture was heated to reflux, resulting in an internal temperature of 29° C. 7.1 g t-butyl hydroperoxide (70% in water) is added in aliquots during a 9 h time frame. The internal temperature reached 52° C. at the end. The reaction mixture showed a single liquid phase and some solids. The liquid was analyzed by GC and indicated a content of 223 g of C3F7OCHFCF2CH2OH which corresponded to a yield of 75%.
- Distillation of the reaction mixture resulted in 171 g of product (bp 54° C./23 mbar) corresponding to an isolated yield of 57%.
- b. Preparation of C3F7OCHFCF2COONH4
- A 2 liter glass flask equipped with a thermometer, reflux condenser, dropping funnel and stirrer was used. 674 g water, 136 g KMnO4, and 38 g NaOH are placed in the flask. 169 g C3F7OCHFCF2CH2OH were added to the well stirred mixture via the dropping funnel. The temperature is held below 50° C. Residual permanganate was destroyed by addition of a small amount of methanol. The resulting slurry was filtered to remove the MnO2. After washing the filter cake with water, the combined filtrate was transferred to a distillation apparatus and acidified with 65 g of sulfuric acid. 100 g methanol was added and a flash distillation was started. The distillate formed two layers. The lower layer was separated and the upper layer returned to the distillation pot. In total 182 g lower layer were collected. Fractionation of the crude ester resulted in 137 g of C3F7OCHFCF2COOCH3 with a boiling point of 55-56° C./52 mbar. This corresponds to a yield of 77%.
- The ester was converted to the ammonium salt by saponification with aqueous ammonia and subsequent removal of methanol by distillation.
- A sample of diacid fluoride, FCOCF(CF3)—O—(CF2)5COF (500 g, 1.1 mol) prepared from the hexafluoropropylene oxide (HFPO) coupling of perfluoroadipoyl fluoride as described in US Pub. No. US 2004/0116742 and was added over 2 hours to a stirred slurry of sodium carbonate (500 g, 4.7 mol) in 500 g of diglyme at 85° C. to make the disalt. The reaction liberated CO2 gas. Distilled water (25 g, 1.4 mol) was added at 85° C. The mixture was heated up to 168° C. with CO2 off-gassing and held for 30 minutes. The reaction was cooled down and sulfuric acid (350 g, 3.6 mol) in 1100 g of water was added to make the reaction mixture acidic. Bottom phase was washed with 400 g of 50% sulfuric acid and vacuum distilled to give CF3—CFH—O—(CF2)5COOH 426 g, 1.0 mol for a 95% yield having a boiling point of 132-135° C./15 mm. This was followed by the addition of 46 g NaOH in 63 g of water. The salts were dried in a vacuum oven at 112° C./15 mm Hg to give 386 g of slight yellow sticky solids. To the salt was added sulfuric acid and the lower fluorochemical phase was vacuum distilled. The previous process was repeated two more times to yield a colorless acid. The surfactant CF3—CFH—O—(CF2)5COONH4 having a melting point of 159-165° C. was made quantitatively from the reaction of 200 g of acid reacted with excess ammonium hydroxide and dried.
- A sample of diacid fluoride, FCOCF(CF3)—O—(CF2)3COF (503 g, 1.4 mol) prepared from the HFPO coupling of perfluorosuccinyl fluoride as described in US Pub. No. US 2004/0116742 and was added over 2 hours to a stirred slurry of sodium carbonate (387 g, 3.7 mol) in 650 g of diglyme at 78° C. to make the disalt. The reaction liberated CO2 gas. Distilled water (35 g, 1.9 mol) was added at 85° C. The mixture was heated up to 165° C. with CO2 off-gassing and held for 30 minutes. Reaction was cooled down and sulfuric acid (250 g, 2.6 mol) in 1250 g of water was added to make the reaction mixture acidic. To the bottom phase was added 60 g NaOH in 60 g of water. Dried the salt in vacuum oven at 112° C./15 mm and recovered 450 g. To the salt was added 300 g of 50% sulfuric acid and the lower fluorochemical phase was washed once with 200 g of 50% sulfuric acid. Vacuum distillation gave CF3—CFH—O—(CF2)3COOH (400 g, 1.3 mol) for a 95% yield having a boiling point of 111° C./15 mm Hg. The acid was treated with caustic followed by sulfuric acid and vacuum distilled. This was repeated a second time to yield a colorless acid. The surfactant CF3—CFH—O—(CF2)3COONH4 having a melting point of 64-68° C. was made quantitatively from the reaction of 208 g of acid reacted with excess ammonium hydroxide and dried.
- Preparation of Compound 6: C3F7—O—C2HF3—O—CH2—COONH4
- A mixture of 320 ml Tetrahydrofurane, 40 g Hydroxy acetic methylester and 188 g PPVE is cooled to 0° C., 27 g KOH-powder are added in small portions—during the addition of KOH, the reaction mixture heats up to 60° C. After the addition of KOH, the whole reaction mixture is agitated for 6 h at 25° C. The precipitated salt is separated by filtration, dissolved in 300 ml water and then treated with 57 g H2SO4 (conc). The resulting mixture separates in two layers; the lower phase is C3F7—O—C2HF3—O—CH2—COOH, 86 g (56%). The distilled acid (bp. 125° C., 20 mbar) is neutralized with 25% aqueous ammonia solution to provide a 30% solution in water.
- A 2 liter glass flask equipped with a mechanical stirrer, thermometer and reflux condenser (−80° C.) is used. Heating of the flask is provided by an electric heating mantle. The conversion is carried out as a one pot reaction. 275 g perfluoropropyl vinyl ether (PPVE), 280 g KOH, 602 g water, 151 g t-butanol, and 10 g methyl trioctyl ammonium chloride are placed in the flask. The three phase mixture is subjected to vigorous stirring. After initial heating a moderate exothermic reaction occurs. Mixing is continued for nine hours. During this time the internal temperature adjusts to 27-33° C. Mixing is stopped when the exothermic reaction ceases. The reaction mixture forms two layers. The low temperature reflux condenser is replaced by a standard reflux condenser. Sulfuric acid (392 g) is slowly added without external cooling. The batch is heated to reflux. Unreacted PPVE is vented. At about 80° C. internal temperature gas begins to evolve. Heating is continued until the gas evolution has ceased. At this time the internal temperature reaches 101° C. The batch is cooled to RT and the reflux condenser is replaced by a distillation device. No column is used. 110 g methanol is added to the batch and distillation is started. The condensed vapors form two layers. The lower layer is separated and the upper layer is returned to the flask. Distillation is stopped when no more lower phase is formed. In total, 234 g of lower phase are collected. Fractionation of the lower phase yields 167 g of C3F7OCHFCOOCH3 with a boiling point of 120-122° C. at ambient pressure.
- The calculated yield was 59% based on total PPVE used; 70% based on converted PPVE. The ester is converted to the ammonium salt by reaction with aqueous ammonia. Methanol is removed by fractionated distillation. The resulting aqueous solution is used as an emulsifier in the polymerization of fluorinated olefins.
- Oxidation of perfluorinated vinyl ethers with oxygen in the presence of SbF5 was carried out as described in U.S. Pat. No. 4,987,254. The initially formed acid fluorides were esterified with methanol and purified by distillation. The distilled esters were converted to the corresponding ammonium salts by saponification with aqueous ammonia. A dry flask equipped with a magnetic stirrer bar, thermometer, dry ice reflux condenser, dropping funnel, and gas inlet tube was charged with 5 g of graphite. The flask was flushed with nitrogen and 332 g of CF3OCF2CF2CF2OCF═CF2 were added at room temperature. 2.6 g of SbF5 was added via the dropping funnel and oxygen was charged in the flask at ambient pressure. An exothermic reaction indicated the oxidation. Total reaction time was 14 hours. After the first hour, 2.6 g and after 7 hours, 3.5 g of SbF5 were added. Esterification was achieved by slow addition of 50 g of methanol to the reaction mixture. The resulting ester was isolated from the batch by flash distillation after addition of 300 g water and 50 g methanol. The distillate formed two phases. The lower phase was separated and the upper phase returned to the flask. 310 g of lower phase were collected. GC analysis showed a content of 52% of CF3OCF2CF2CF2OCF2COOCH3. Purification via fractionated distillation resulted in 144 g of pure ester with a boiling point of 51° C. at 52 mbar.
- CF3OCF2CF2COOCH3 was isolated as a by-product. Saponification of the ester with aqueous ammonia at 60 to 80° C. and removal of methanol by distillation resulted in an aqueous solution of CF3OCF2CF2CF2OCF2COONH4. All structures were confirmed by 19F-NMR spectra.
- Compound C-3 was synthesized by reaction of perfluorobutyric acid fluoride with tetrafluorooxethane and fluorination of the CH2 group before conversion to the ammonium salts per WO 2005/003075.
- The perfluorinated and partially fluorinated carboxylates were evaluated for urinary clearance using a pharmacokinetic study in rats. The goal was to measure the total amount of parent compound eliminated via urinary output and estimate the rate of elimination. The study was approved by the IACUC (Institutional Animal Care and Use Committees) and was performed in 3M Company's AAALAC (Association for Assessment and Accreditation of Laboratory Animal Care )—accredited facility.
- The study utilized male Sprague Dawley rats, 6 to 8 weeks of age, and approximately 200 to 250 g body weight at study onset. The test compounds of table 2 were administered at a dose of 73 micro Moles per kg body weight in rats (N=3 animals per tested compound). All test compounds were prepared in sterile deionized water and given to rats via oral gavage. After test compounds administration, the rats were housed individually in metabolism cages for urine collection: 0 to 6 hours, 6 to 24 hours, 24 to 48 hours and 72 to 96 hours. Animals were observed throughout the study for clinical signs of toxicity. Gross necropsy was performed at the termination of each study (96 hours post-dose) with sera and liver samples being retained from each animal.
- The concentration of the parent compound or metabolites thereof were quantitatively measured via fluorine NMR on each urine sample for each animal at each time point based on internally added standards.
- The bioaccumulation data obtained in accordance with the above test are reported in table 2.
-
TABLE 2 % Recovery Compound-related T½ (h) (96 h) Effects C-1 ~550 6 Hepatomegaly C-2 10 73 — C-3 31 42 Hepatomegaly Compound 1 12 84 — Compound 2 11 95 Compound 3 11 94 — Compound 4 24 32 Hepatomegaly Compound 5 8 95 — Compound 6 13* 65* — *No parent compound observed in the urine. T½ and % recovery are based on elimination of the major metabolite —C3F7—O—CHFCOO−. T1/2 is the renal half-life and is the time required for the amount of a particular substance in a biological system to be reduced to one half of its value by biological processes when the rate of removal is approximately exponential. In theseexamples the value of T1/2 is calculated by exponential least squares curve fitting (y = AeBx and T1/2 = 0.693/B) where y represents the concentration of analyte in urine and x represents time in hours. -
TABLE 3 C-1 C-2 C-3 1 2 3 4* 5 6 7* Polymerization 101 74 72 82 82 83 75 78 174 135 time (min) Average 111 110 113 126 108 128 127 105 139 136 Particle Size (nm) SSG 2.166 2.169 2.165 2.168 2.167 2.164 2.151 2.154 2.210 2.190 (g/cm3) Solid content 9.9 10.3 10.2 10.2 10.3 10.2 8.1 10.0 10.0 10.1 (w-%) *140 mmol
Claims (20)
Rf—O-L-CO2— (I)
Rf—O-L-CO2— (I)
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